Geopolymer cement slurries, cured geopolymer cement and methods of making and use thereof

ABSTRACT

Geopolymer cement slurries, cured geopolymer cements, and methods of making cured geopolymer cement and methods of using geopolymer cement slurries are provided. The geopolymer cement slurry comprises Saudi Arabian volcanic ash, an aqueous solution, Na2SiO3, NaOH, and a resin. The Saudi Arabian volcanic ash comprises SO3, CaO, SiO2, Al2O3, Fe2O3, MgO, and K2O.

TECHNICAL FIELD

Embodiments of the present disclosure generally relate to geopolymer cement slurries and methods of making and using geopolymer cement slurries and to cured geopolymer cements and methods of making cured geopolymer cement.

BACKGROUND

Cement slurries are used in the oil and gas industries, such as for cementing in oil and gas wells. Primary, remedial, squeeze, and plug cementing techniques can be used, for instance, to place cement sheaths in an annulus between casing and well formations, for well repairs, well stability, and for well abandonment (sealing an old well to eliminate safety hazards). These cement slurries must be able to consistently perform over a wide range of temperatures and pressures, in the presence of certain corrosive chemical species, and under challenging mechanical conditions, as oil and gas wells can be located in a multitude of diverse locations. For example, a cement slurry may be used in conditions of less than 0° C. in freezing permafrost zones, and in temperatures exceeding 400° C. in geothermal wells and, as such, must be able to properly set under an assortment of conditions.

Proper placement of a cement slurry can be vital to wellbore isolation. However, conventional cement solutions may have a density greater than 170 pounds per cubic feet (lb/ft), and a yield point of less than 20 pounds force per 100 square feet (lb/100 ft²), leading to inconsistent flowability and creating concerns when handling or pumping the cement, as uniform placement of the slurry can be quite difficult. Moreover, cement slurries with a greater density increase the hydrostatic pressure that the cement column exerts on the wellbore, leading to poor isolation in weak zones that may break or crack under pressure. Cement slurries with a reduced density and increased yield point allow for more uniform flowability and more accurate and precise placement of the cement. Furthermore, cement slurries with a reduced density may be placed in a single stage, eliminating the need for multistage cementing tools.

SUMMARY

Accordingly, there is an ongoing need for cement slurries having a reduced density and an increased yield point. The present embodiments address these needs by providing geopolymer cement slurries and methods of making and using geopolymer cement slurries that include Saudi Arabian volcanic ash to serve as an extender to decrease the density and increase the yield point of the cement.

In one embodiment, a geopolymer cement slurry is provided, comprising an aqueous solution, Saudi Arabian volcanic ash, Na₂SiO₃, NaOH, and a resin. The Saudi Arabian volcanic ash comprises SO₃, CaO, SiO₂, Al₂O₃, Fe₂O₃, MgO, and K₂O.

Additional features and advantages of the described embodiments will be set forth in the detailed description which follows, and in part will be readily apparent to those skilled in the art from that description or recognized by practicing the described embodiments, including the detailed description which follows as well as the claims.

DETAILED DESCRIPTION

As used throughout this disclosure, the term “geopolymer cement slurry” refers to a composition comprising Saudi Arabian volcanic ash that is mixed with at least water to form cement. The geopolymer cement slurry may contain calcined alumina (Al₂O₃), silica (SiO₂), calcium oxide (CaO, also known as lime), iron oxide (Fe₂O₃), magnesium oxide (MgO), clay, sand, gravel, and mixtures thereof.

As used throughout this disclosure, the term “consistency” refers to a rheological property of matter related to the cohesion of the individual particles of a given material, its ability to deform and its resistance to flow. The consistency of geopolymer cement slurries is determined by thickening time tests in accordance with API Recommended Practice 10B and is expressed in Bearden units of consistency (Bc), a dimensionless quantity with no direction conversion factor to more common units of viscosity. The Bearden units of consistency is measured on a scale from 1 to 100 where, conventionally, difficult pumping is thought to begin at 50 Bc, and cement is completely set at 100 Bc.

As used throughout this disclosure, the term “curing” refers to providing adequate moisture, temperature and time to allow the concrete to achieve the desired properties (such as hardness) for its intended use through one or more reactions between the water and the Saudi Arabian volcanic ash.

As used throughout this disclosure, the term “drying” refers to merely allowing the cement to achieve a moisture condition appropriate for its intended use, which may only involve physical state changes, as opposed to chemical reactions.

As used throughout this disclosure, the term “extender” refers to a cement extender, that is, a chemical additive or inert material used to decrease the density of a geopolymer cement slurry and increase the yield point. Reducing the slurry density reduces the hydrostatic pressure of the cement column in the wellbore, leading to successful wellbore isolation.

As used throughout this disclosure, the term “free of” as used to describe any chemical or component refers to not including more than trace amounts of the chemical or component, where trace amounts refers to having less than 0.1% of the chemical or component.

As used throughout this disclosure, the term “kick” is used to describe a flow of formation fluids into the wellbore during drilling operations. The kick is physically caused by the pressure in the wellbore being less than that of the formation fluids, thus causing flow. This condition of lower wellbore pressure than the formation is caused in two ways. First, if the mud weight is too low, then the hydrostatic pressure exerted on the formation by the fluid column may be insufficient to hold the formation fluid in the formation. This can happen if the mud density is suddenly decreased or if a drilled formation has a higher pressure than anticipated. This type of kick might be called an underbalanced kick. The second way a kick can occur is if dynamic and transient fluid pressure effects, usually due to motion of the drillstring or casing, effectively lower the pressure in the wellbore below that of the formation. This second kick type could be called an induced kick.

As used throughout this disclosure, the term “plastic viscosity” refers to the slope of the shear stress/shear rate line greater than the yield point. Plastic viscosity represents the viscosity of a fluid when extrapolated to infinite shear rate. Plastic viscosity is increased by a viscous base fluid and by excess colloidal solids.

As used throughout this disclosure, the term “point of departure” refers to the beginning of thickening of a geopolymer cement slurry during the thickening-time test, and is often abbreviated as POD. For some geopolymer cement slurries, the POD is used as the thickening time.

As used throughout this disclosure, the term “retarder” refers to a chemical agent used to increase the thickening time of geopolymer cement slurries to enable proper placement. The need for cement retardation increases with depth due to the greater time required to complete the cementing operation and the effect of increased temperature on the cement-setting process.

As used throughout this disclosure, the term “Saudi Arabian volcanic ash” refers to volcanic ash originally acquired from Saudi Arabia.

As used throughout this disclosure, the term “shear stress” refers to the force per unit area required to sustain a constant rate of fluid movement.

As used throughout this disclosure, the term “shear rate” refers to the rate of change of velocity at which one layer of fluid passes over an adjacent layer.

As used throughout this disclosure, the term “subsurface formation” refers to a body of rock that is sufficiently distinctive and continuous from the surrounding rock bodies that the body of rock can be mapped as a distinct entity. A subsurface formation is, therefore, sufficiently homogenous to form a single identifiable unit containing similar rheological properties throughout the subsurface formation, including, but not limited to, porosity and permeability. A subsurface formation is the fundamental unit of lithostratigraphy.

As used throughout this disclosure, the term “thickening time” refers to a measurement of the time during which a geopolymer cement slurry remains in a fluid state and is capable of being pumped. Thickening time is assessed under downhole conditions using a pressurized consistometer that plots the viscosity of a slurry over time under the anticipated temperature and pressure conditions. The end of the thickening time is conventionally about 50 or 70 Bc.

As used throughout this disclosure, the term “wellbore” refers to the drilled hole or borehole, including the openhole or uncased portion of the well. Borehole may refer to the inside diameter of the wellbore wall, the rock face that bounds the drilled hole.

As used throughout this disclosure, the term “yield point” refers to the point in the stress-strain curve at which the curve levels off and plastic deformation begins to occur. Yield point is used to evaluate the void filling properties of cements and the ability of a cement to flow through the annulus. A greater yield point implies a non-Newtonian fluid, one that flows more uniformly than a fluid of similar density but lesser yield point. Yield point is increased by adding freshly dispersed clay or a flocculant, such as lime.

Embodiments of the present disclosure also relate to methods of producing and using geopolymer cement slurries, in some particular embodiments, for use in the oil and gas industries, such as for cementing in oil and gas wells. Oil and gas wells may be formed in subsurface formations. The wellbore may serve to connect natural resources, such as petrochemical products, to a ground level surface. In some embodiments, a wellbore may be formed in the subsurface formation, which may be formed by a drilling procedure. To drill a subterranean well or wellbore, a drill string including a drill bit and drill collars to weight the drill bit is inserted into a predrilled hole and rotated to cut into the rock at the bottom of the hole, producing rock cuttings. Commonly, drilling fluid may be utilized during the drilling process. To remove the rock cuttings from the bottom of the wellbore, drilling fluid is pumped down through the drill string to the drill bit. The drilling fluid cools the drill bit and lifts the rock cuttings away from the drill bit and carries the rock cuttings upwards as the drilling fluid is recirculated back to the surface.

In some instances, a casing may be inserted into the wellbore. The casing may be a pipe or other tubular structure which has a diameter less than that of the wellbore. Generally, the casing may be lowered into the wellbore such that the bottom of the casing reaches to a region near the bottom of the wellbore. In some embodiments, the casing may be cemented by inserting a cement slurry into the annulus region between the outer edge of the casing and the edge of the wellbore (the surface of the subsurface formation). The geopolymer cement slurry of the present disclosure may be inserted into the annular region by pumping the geopolymer cement slurry into the interior portion of the casing, to the bottom of the casing, around the bottom of the casing, into the annular region, or a combination of some or all of these. The geopolymer cement slurry may displace the drilling fluid, pushing it to the top of the well. In some embodiments, a spacer fluid may be used as a buffer between the geopolymer cement slurry and the drilling fluid by displacing and removing the drilling fluid before the geopolymer cement slurry is pumped into the well to prevent contact between the drilling fluid and the geopolymer cement slurry. Following the insertion of an appropriate amount of geopolymer cement slurry into the interior region of the casing, in some embodiments, a displacement fluid may be utilized to push the geopolymer cement slurry out of the interior region of the casing and into the annular region. This displacement may cause the entirety of the spacer fluid and drilling fluid to be removed from the annular region, out the top of the wellbore. The geopolymer cement slurry may then be cured or otherwise allowed to harden.

To ensure the stability and safety of a well, it is important that the geopolymer cement slurry properly harden into cured geopolymer cement. If the geopolymer cement slurry is not evenly placed or fluid is lost from the geopolymer cement slurry before curing, the geopolymer cement slurry may not evenly harden into a cured geopolymer cement. Therefore, the density, viscosity, flowability, and thickening time of a geopolymer cement slurry are important properties to ensure proper placement. Specifically, thickening time may be retarded by the use of retarder additives, creating more time for optimal placement of the cement before setting. Similarly, reducing fluid loss from the geopolymer cement slurry ensures uniform hardening, as curing often involves water-based reactions with the geopolymer cement slurry. Too much or too little water affects the hardness and, thus, the quality of the cured geopolymer cement produced.

A number of conditions may impact the fluid loss of a geopolymer cement slurry. For instance, water may be drawn from the slurry into the permeable subsurface formation, particularly if pumping ceases and the slurry becomes static without hardening. Water may also be lost due to displacement as the geopolymer cement slurry is passed through constrictions, such as the tight clearance between a casing and an annulus, which may “squeeze” water from the slurry. Adverse weather and soil conditions may additionally impact the amount of water present in the geopolymer cement slurry. As such, control of fluid loss of the geopolymer cement slurry may allow for a more uniform and stronger cured geopolymer cement.

To ensure the stability and safety of a well, it is important that the cured geopolymer cement maintains integrity and isolates the wellbore from the surrounding subsurface formations. If the cement cracks or degrades under cyclic stresses, wellbore integrity and isolation may be lost, resulting in undesirable fluid communication between the wellbore and surrounding subsurface formations. Not intending to be limited by theory, this fluid communication may result in drilling fluid loss from the wellbore into the surrounding subsurface formation, or in decreased wellbore pressure, possibly leading to a well control event. Therefore, wellbore integrity and isolation are critical to efficient production and use of a wellbore.

The present disclosure provides methods of making geopolymer cement slurries which may have, among other attributes, reduced density, increased yield point, improved mechanical properties, and increased resistance to H₂S to address these concerns. The method of making the geopolymer cement slurry of the present disclosure includes mixing Saudi Arabian volcanic ash, and an aqueous solution to form the geopolymer cement slurry, in which the Saudi Arabian volcanic ash comprises SO₃, CaO, SiO₂, Al₂O₃, Fe₂O₃, MgO, and K₂O and the geopolymer cement slurry is free of any other SiO₂ additive. Without being bound by any particular theory, use of Saudi Arabian volcanic ash may provide the cured geopolymer cement with increased yield point, reduced density, improved mechanical properties, and increased resistance to H₂S of the geopolymer cement slurry.

The mixing step, in some embodiments, may involve shearing the aqueous solution, and Saudi Arabian volcanic ash and, optionally, other additives at a suitable speed for a suitable period of time to form the geopolymer cement slurry. In one embodiment, the mixing may be done in the lab using a standard API blender for 15 seconds at 4,000 revolutions per minute (rpm) and 35 seconds at 12,000 rpm. The equation of mixing energy is:

$\begin{matrix} {\frac{E}{M} = \frac{k\;\omega^{2}t}{V}} & \left( {{Equation}\mspace{14mu} 1} \right) \end{matrix}$

Where

E=Mixing energy (kiloJoules (kJ)) M=Mass of slurry (kilograms (kg)) k=6.1×10⁻⁸ m⁵/s (constant found experimentally) ω=Rotational speed (radians/second (s⁻¹)) t=Mixing time (s) V=Slurry volume (m³)

An aqueous solution may be added to the Saudi Arabian volcanic ash to produce the slurry. The aqueous solution may include one or more than one of deionized water, tap water, fresh water, salt water, natural or synthetic brine, municipal water, formation water, produced water, well water, filtered water, distilled water, sea water, other type of water, or combinations of waters. In some embodiments, the aqueous solution may include water or a solution containing water and one or more inorganic compounds dissolved in the water or otherwise completely miscible with the water. In some embodiments, the aqueous solution may contain brine, including natural and synthetic brine. In some embodiments, salt or other organic compounds may be incorporated into the aqueous solution to control certain properties of the water, and thus the geopolymer cement slurry, such as density. Without being bound by any particular theory, increasing the saturation of the aqueous solution by increasing the salt concentration or the level of other organic compounds in the water may increase the density of the water, and thus, the geopolymer cement slurry. Suitable salts may include, but are not limited to, alkali metal chlorides, hydroxides, or carboxylates. In some embodiments, suitable salts may include sodium, calcium, cesium, zinc, aluminum, magnesium, potassium, strontium, silicon, lithium, chlorides, bromides, carbonates, iodides, chlorates, bromates, formates, nitrates, sulfates, phosphates, oxides, fluorides, and combinations of these.

In some embodiments, the geopolymer cement slurry may contain from 10 to 70 weight percent (wt. %) by weight of volcanic ash (BWOV) aqueous solution. In some embodiments, the geopolymer cement slurry may contain from 10 to 40 wt. %, from 10 to 30 wt. %, from 10 to 20 wt. %, from 20 to 40 wt. %, from 25 to 35 wt. %, or from 20 to 30 wt. % BWOV water. The geopolymer cement slurry may contain 30 wt. % BWOV aqueous solution.

Along with the aqueous solution, the geopolymer cement slurry includes Saudi Arabian volcanic ash. The Saudi Arabian volcanic ash functions as an extender, reducing the density of the geopolymer cement slurry and increasing the yield point of the geopolymer cement slurry. In embodiments, the geopolymer cement slurry may include from 30 to 70 wt. %, from 30 to 65 wt. %, from 30 to 60 wt. %, from 30 to 55 wt. %, from 30 to 50 wt. %, from 30 to 45 wt. %, from 30 to 40 wt. %, from 30 to 35 wt. %, from 35 to 70 wt. %, from 35 to 65 wt. %, from 35 to 60 wt. %, from 35 to 55 wt. %, from 35 to 50 wt. %, from 35 to 45 wt. %, from 35 to 40 wt. %, from 40 to 70 wt. %, from 40 to 65 wt. %, from 40 to 60 wt. %, from 40 to 55 wt. %, from 40 to 50 wt. %, from 40 to 45 wt. %, from 45 to 70 wt. %, from 45 to 65 wt. %, from 45 to 60 wt. %, from 45 to 55 wt. %, from 45 to 50 wt. %, from 50 to 70 wt. %, from 50 to 65 wt. %, from 50 to 60 wt. %, from 50 to 55 wt. %, from 55 to 70 wt. %, from 55 to 65 wt. %, from 55 to 60 wt. %, from 60 to 70 wt. %, from 60 to 65 wt. %, or from 65 to 70 wt. % Saudi Arabian volcanic ash by weight of the geopolymer cement slurry.

The Saudi Arabian volcanic ash may have a particle size of from 20 to 30 microns. The Saudi Arabian volcanic ash is free of TiO₂. The Saudi Arabian volcanic ash may comprise from 0.05 to 2 wt. %, from 0.05 to 1 wt. %, from 0.05 to 0.8 wt. %, from 0.05 to 0.5 wt. %, from 0.05 to 0.2 wt. %, from 0.05 to 0.15 wt. %, from 0.05 to 0.1 wt. %, from 0.1 to 2 wt. %, from 0.1 to 1 wt. %, from 0.1 to 0.8 wt. %, from 0.1 to 0.5 wt. %, from 0.1 to 0.2 wt. %, from 0.1 to 0.15 wt. %, from 0.15 to 2 wt. %, from 0.15 to 1 wt. %, from 0.15 to 0.8 wt. %, from 0.15 to 0.5 wt. %, from 0.15 to 0.2 wt. %, from 0.2 to 2 wt. %, from 0.2 to 1 wt. %, from 0.2 to 0.8 wt. %, or from 0.2 to 0.5 wt. % SO₃. More specifically, the Saudi Arabian volcanic ash may comprise from 0.05 to 0.2 wt. % SO₃, from 5 to 10 wt. % CaO, from 40 to 50 wt. % SiO₂, from 10 to 20 wt. % Al₂O₃, from 10 to 15 wt. % Fe₂O₃, from 5 to 10 wt. % MgO, and from 0.5 to 5 wt. % K₂O. The geopolymer cement slurry may include from 2 to 80 wt. % BWOV, from 5 to 80 wt. % BWOV, from 8 to 80 wt. % BWOV, from 15 to 80 wt. % BWOV, from 25 to 80 wt. % BWOV, from 40 to 80 wt. % BWOV, from 50 to 80 wt. % BWOV, from 60 to 80 wt. % BWOV, from 2 to 60 wt. % BWOV, from 5 to 60 wt. % BWOV, from 8 to 60 wt. % BWOV, from 15 to 60 wt. % BWOV, from 25 to 60 wt. % BWOV, from 40 to 60 wt. % BWOV, from 50 to 60 wt. % BWOV, from 2 to 50 wt. % BWOV, from 5 to 50 wt. % BWOV, from 8 to 50 wt. % BWOV, from 15 to 50 wt. % BWOV, from 25 to 50 wt. % BWOV, from 40 to 50 wt. % BWOV, from 2 to 40 wt. % BWOV, from 5 to 40 wt. % BWOV, from 8 to 40 wt. % BWOV, from 15 to 40 wt. % BWOV, from 25 to 40 wt. % BWOV, from 2 to 25 wt. % BWOV, from 5 to 25 wt. % BWOV, from 8 to 25 wt. % BWOV, from 15 to 25 wt. % BWOV, from 2 to 15 wt. % BWOV, from 5 to 15 wt. % BWOV, from 8 to 15 wt. % BWOV, from 2 to 8 wt. % BWOV, or from 5 to 8 wt. % BWOV Saudi Arabian volcanic ash.

The Saudi Arabian volcanic ash may comprise from 2 to 25 wt. %, from 2 to 20 wt. %, from 2 to 15 wt. %, from 2 to 10 wt. %, from 2 to 8 wt. %, from 2 to 5 wt. %, from 5 to 25 wt. %, from 5 to 20 wt. %, from 5 to 15 wt. %, from 5 to 10 wt. %, from 5 to 8 wt. %, from 8 to 25 wt. %, from 8 to 20 wt. %, from 8 to 15 wt. %, from 8 to 10 wt. %, from 10 to 25 wt. %, from 10 to 20 wt. %, or from 10 to 15 wt. % CaO. The Saudi Arabian volcanic ash may comprise from 30 to 70 wt. %, from 30 to 60 wt. %, from 30 to 55 wt. %, from 30 to 50 wt. %, from 30 to 45 wt. %, from 30 to 40 wt. %, from 35 to 70 wt. %, from 35 to 60 wt. %, from 35 to 55 wt. %, from 35 to 50 wt. %, from 35 to 45 wt. %, from 35 to 40 wt. %, from 40 to 70 wt. %, from 40 to 60 wt. %, from 40 to 55 wt. %, from 40 to 50 wt. %, from 40 to 45 wt. %, from 45 to 70 wt. %, from 45 to 60 wt. %, from 45 to 55 wt. %, from 45 to 50 wt. %, from 50 to 70 wt. %, from 50 to 60 wt. %, or from 50 to 55 wt. % SiO₂. The Saudi Arabian volcanic ash may comprise from 2 to 40 wt. %, from 2 to 35 wt. %, from 2 to 30 wt. %, from 2 to 25 wt. %, from 2 to 20 wt. %, from 2 to 15 wt. %, from 2 to 10 wt. %, from 2 to 5 wt. %, from 5 to 40 wt. %, from 5 to 35 wt. %, from 5 to 30 wt. %, from 5 to 25 wt. %, from 5 to 20 wt. %, from 5 to 15 wt. %, from 5 to 10 wt. %, from 10 to 40 wt. %, from 10 to 35 wt. %, from 10 to 30 wt. %, from 10 to 25 wt. %, from 10 to 20 wt. %, from 10 to 15 wt. %, from 15 to 40 wt. %, from 15 to 35 wt. %, from 15 to 30 wt. %, from 15 to 25 wt. %, from 15 to 20 wt. %, from 20 to 40 wt. %, from 20 to 35 wt. %, from 20 to 30 wt. %, from 20 to 25 wt. % Al₂O₃. The Saudi Arabian volcanic ash may comprise from 2 to 30 wt. %, from 2 to 25 wt. %, from 2 to 20 wt. %, from 2 to 15 wt. %, from 2 to 13 wt. %, from 2 to 10 wt. %, from 2 to 8 wt. %, from 2 to 5 wt. %, from 5 to 30 wt. %, from 5 to 25 wt. %, from 5 to 20 wt. %, from 5 to 15 wt. %, from 5 to 13 wt. %, from 5 to 10 wt. %, from 5 to 8 wt. %, from 8 to 30 wt. %, from 8 to 25 wt. %, from 8 to 20 wt. %, from 8 to 15 wt. %, from 8 to 13 wt. %, from 8 to 10 wt. %, from 10 to 30 wt. %, from 10 to 25 wt. %, from 10 to 20 wt. %, from 10 to 15 wt. %, from 10 to 13 wt. %, from 13 to 30 wt. %, from 13 to 25 wt. %, from 13 to 20 wt. %, from 13 to 15 wt. %, from 15 to 30 wt. %, from 15 to 25 wt. %, or from 15 to 20 wt. % Fe₂O₃. The Saudi Arabian volcanic ash may comprise from 2 to 25 wt. %, from 2 to 20 wt. %, from 2 to 15 wt. %, from 2 to 10 wt. %, from 2 to 8 wt. %, from 2 to 5 wt. %, from 5 to 25 wt. %, from 5 to 20 wt. %, from 5 to 15 wt. %, from 5 to 10 wt. %, from 5 to 8 wt. %, from 8 to 25 wt. %, from 8 to 20 wt. %, from 8 to 15 wt. %, from 8 to 10 wt. %, from 10 to 25 wt. %, from 10 to 20 wt. %, or from 10 to 15 wt. % MgO. The Saudi Arabian volcanic ash may comprise from 0.2 to 10 wt. %, from 0.2 to 7 wt. %, from 0.2 to 5 wt. %, from 0.2 to 3 wt. %, from 0.2 to 2 wt. %, from 0.2 to 1 wt. %, from 0.2 to 0.5 wt. %, from 0.5 to 10 wt. %, from 0.5 to 7 wt. %, from 0.5 to 5 wt. %, from 0.5 to 3 wt. %, from 0.5 to 2 wt. %, from 0.5 to 1 wt. %, from 1 to 10 wt. %, from 1 to 7 wt. %, from 1 to 5 wt. %, from 1 to 3 wt. %, from 1 to 2 wt. %, from 2 to 10 wt. %, from 2 to 7 wt. %, from 2 to 5 wt. %, from 1 to 3 wt. %, from 3 to 10 wt. %, from 3 to 7 wt. %, from 3 to 5 wt. %, from 5 to 10 wt. %, or from 5 to 7 wt. % K₂O.

Along with the aqueous solution and Saudi Arabian volcanic ash, the geopolymer cement slurry includes sodium silicate (Na₂SiO₃). The geopolymer cement slurry may include from 25 to 50 wt. %, from 25 to 45 wt. %, from 25 to 40 wt. %, from 25 to 35 wt. %, from 25 to 30 wt. %, from 30 to 50 wt. %, from 30 to 45 wt. %, from 30 to 40 wt. %, from 30 to 35 wt. %, from 35 to 50 wt. %, from 35 to 45 wt. %, from 35 to 40 wt. %, from 40 to 50 wt. %, from 40 to 45 wt. %, or from 45 to 50 wt. % Na₂SiO₃. The Na₂SiO₃ may have a ratio of Na₂O to SiO₂ of from 0.250:1 to 0.350:1, from 0.250:1 to 0.330:1, from 0.250:1 to 0.300:1, from 0.250:1 to 0.270:1, from 0.270:1 to 0.350:1, from 0.270:1 to 0.330:1, from 0.270:1 to 0.300:1, from 0.300:1 to 0.350:1, from 0.300:1 to 0.330:1, or from 0.330:1 to 0.350:1.

Along with the aqueous solution and Saudi Arabian volcanic ash, the geopolymer cement slurry includes sodium hydroxide (NaOH). The geopolymer cement slurry may include from 15 to 35 wt. %, from 15 to 30 wt. %, from 15 to 25 wt. %, from 15 to 20 wt. %, from 20 to 35 wt. %, from 20 to 30 wt. %, from 20 to 25 wt. %, from 25 to 35 wt. %, from 25 to 30 wt. %, or from 30 to 35 wt. % NaOH.

The geopolymer cement slurry may have a pH of greater than 7. In embodiments, the geopolymer cement slurry may have a pH of from 8 to 14, from 9 to 13, from 10 to 13, from 11 to 13, from 11.5 to 13.0, from 11.6 to 13.0, from 11.6 to 12.5, or from 11.6 to 12.0. In embodiments, NaOH may be used as a pH control additive such that the activation solution has a pH of from 7 to 14, from 7 to 12, from 7 to 11, from 7 to 10, from 7 to 9, from 8 to 14, from 8 to 12, from 8 to 11, from 8 to 10, from 8 to 9, from 9 to 14, from 9 to 12, from 9 to 11, from 9 to 10, from 10 to 14, from 10 to 12, from 10 to 11, from 11 to 14, from 11 to 13, from 11 to 12, from 11.6 to 14, from 11.6 to 13, from 12 to 13, greater than 8, greater than 9, greater than 10, greater than 10.5, greater than 11, or greater than 11.6 when NaOH is present. Without intending to be bound by theory, NaOH may be used as a pH control additive to prevent corrosion in the wellbore. It is contemplated that the alkaline environment (when the pH is as described previously) may dissolve the alumina and silica, and allow for silicon and aluminum tetrahedral to form, thereby forming the geopolymer cement slurry by sharing oxygen atoms. A pH as described previously may accelerate the dissolution of the alumina and silica, thereby accelerating the formation of the geopolymer cement slurry.

In embodiments, the geopolymer cement slurry may include a sodium aluminosilicate hydrate. This sodium aluminosilicate hydrate may be a reaction product of the Saudi Arabian volcanic ash, Na₂SiO₃, and NaOH. Specifically, a polycondensation of silicate and aluminate monomers (from the Saudi Arabian volcanic ash) under alkaline conditions (due to the addition of NaOH and Na₂SiO₃) may occur, forming the sodium aluminosilicate hydrate. In preparing the geopolymer cement slurry, it was expected to be desirable to have approximately a 1.0:1.0 molar ratio of Na₂O combined with NaOH to aluminate (Al₂O₃). It was contemplated that this may balance the negative charge on the Al atom with the sodium ions in the sodium aluminosilicate hydrate structure. However, after preparing a geopolymer cement slurry with a molar ratio of Na₂O and NaOH to Al₂O₃ of 0.97:1.0, the resulting geopolymer cement slurry had an undesirably quick gelation time that would make well cementing difficult. started to be to address this unexpected outcome, the ratio of Na₂O and NaOH to Al₂O₃ in the geopolymer cement slurry of the present disclosure may range from 0.30:1.00 to 0.90:1.00, from 0.30:1.00 to 0.80:1.00, from 0.30:1.00 to 0.75:1.00, from 0.30:1.00 to 0.70:1.00, from 0.30:1.00 to 0.65:1.00, from 0.30:1.00 to 0.60:1.00, from 0.30:1.00 to 0.55:1.00, from 0.30:1.00 to 0.50:1.00, from 0.30:1.00 to 0.40:1.00, from 0.40:1.00 to 0.90:1.00, from 0.40:1.00 to 0.80:1.00, from 0.40:1.00 to 0.75:1.00, from 0.40:1.00 to 0.70:1.00, from 0.40:1.00 to 0.65:1.00, from 0.40:1.00 to 0.60:1.00, from 0.40:1.00 to 0.55:1.00, from 0.40:1.00 to 0.50:1.00, from 0.50:1.00 to 0.90:1.00, from 0.50:1.00 to 0.80:1.00, from 0.50:1.00 to 0.75:1.00, from 0.50:1.00 to 0.70:1.00, from 0.50:1.00 to 0.65:1.00, from 0.50:1.00 to 0.60:1.00, from 0.50:1.00 to 0.55:1.00, from 0.55:1.00 to 0.90:1.00, from 0.55:1.00 to 0.80:1.00, from 0.55:1.00 to 0.75:1.00, from 0.55:1.00 to 0.70:1.00, from 0.55:1.00 to 0.65:1.00, from 0.55:1.00 to 0.60:1.00, from 0.60:1.00 to 0.90:1.00, from 0.60:1.00 to 0.80:1.00, from 0.60:1.00 to 0.75:1.00, from 0.60:1.00 to 0.70:1.00, from 0.60:1.00 to 0.65:1.00, from 0.65:1.00 to 0.90:1.00, from 0.65:1.00 to 0.80:1.00, from 0.65:1.00 to 0.75:1.00, from 0.65:1.00 to 0.70:1.00, from 0.70:1.00 to 0.90:1.00, from 0.70:1.00 to 0.80:1.00, from 0.70:1.00 to 0.75:1.00, from 0.75:1.00 to 0.90:1.00, from 0.75:1.00 to 0.80:1.00, or from 0.80:1.00 to 0.90:1.00.

In embodiments, the ratio of Na₂SiO₃ combined with NaOH to Al₂O₃ may range from 0.5:1.0 to 9.0:1.0, from 0.5:1.0 to 7.0:1.0, from 0.5:1.0 to 5.0:1.0, from 0.5:1.0 to 3.0:1.0, from 0.5:1.0 to 2.0:1.0, from 0.5:1.0 to 1.5:1.0, from 0.5:1.0 to 1.0:1.0, from 1.0:1.0 to 9.0:1.0, from 1.0:1.0 to 7.0:1.0, from 1.0:1.0 to 5.0:1.0, from 1.0:1.0 to 3.0:1.0, from 1.0:1.0 to 2.0:1.0, from 1.0:1.0 to 1.5:1.0, from 1.5:1.0 to 9.0:1.0, from 1.5:1.0 to 7.0:1.0, from 1.5:1.0 to 5.0:1.0, from 1.5:1.0 to 3.0:1.0, from 1.5:1.0 to 2.0:1.0, from 2.0:1.0 to 9.0:1.0, from 2.0:1.0 to 7.0:1.0, from 2.0:1.0 to 5.0:1.0, from 2.0:1.0 to 3.0:1.0, from 3.0:1.0 to 9.0:1.0, from 3.0:1.0 to 7.0:1.0, from 3.0:1.0 to 5.0:1.0, from 5.0:1.0 to 9.0:1.0, from 5.0:1.0 to 7.0:1.0, or from 7.0:1.0 to 9.0:1.0.

The sodium aluminosilicate hydrate may have a formula of Na_(n) [(—SiO₂)_(z)—AlO₂]_(n) y H₂O, where n represents a degree of polymerization ranging from 1 to 50, from 1 to 40, from 1 to 30, from 1 to 25, from 1 to 20, from 1 to 15, from 1 to 10, from 1 to 5, from 5 to 50, from 5 to 40, from 5 to 30, from 5 to 25, from 5 to 20, from 5 to 15, from 5 to 10, from 10 to 50, from 10 to 40, from 10 to 30, from 10 to 25, from 10 to 20, from 10 to 15, from 15 to 50, from 15 to 40, from 15 to 30, from 15 to 25, from 15 to 20, from 20 to 50, from 20 to 40, from 20 to 30, from 20 to 25, from 25 to 50, from 25 to 40, from 25 to 30, from 30 to 50, from 30 to 40, or from 40 to 50, and z represents an amount of silicate ranging from 2 to 10, from 2 to 8, from 2 to 6, from 2 to 5, from 2 to 4, from 4 to 10, from 4 to 8, from 4 to 6, from 4 to 5, from 5 to 10, from 5 to 8, from 5 to 6, from 6 to 10, from 6 to 8, or from 8 to 10. The sodium aluminosilicate hydrate may have a structure as shown in Structure 1:

The sodium aluminosilicate hydrate may have a compressive strength of from 500 to 5000 psi, from 500 to 3000 psi, from 500 to 2600 psi, from 500 to 2200 psi, from 500 to 2000 psi, from 500 to 1500 psi, from 500 to 1000 psi, from 1000 to 5000 psi, from 1000 to 3000 psi, from 1000 to 2600 psi, from 1000 to 2200 psi, from 1000 to 2000 psi, from 1000 to 1500 psi, from 1500 to 5000 psi, from 1500 to 3000 psi, from 1500 to 2600 psi, from 1500 to 2200 psi, from 1500 to 2000 psi, from 2000 to 5000 psi, from 2000 to 3000 psi, from 2000 to 2600 psi, from 2000 to 2200 psi, from 2200 to 5000 psi, from 2200 to 3000 psi, from 2200 to 2600 psi, from 2600 to 5000 psi, from 2600 to 3000 psi, or from 3000 to 5000 psi.

In some embodiments the geopolymer cement slurry may contain a cement precursor material. The cement precursor material may be any suitable material which, when mixed with water, can be cured into a cement. The cement precursor material may be hydraulic or non-hydraulic. A hydraulic cement precursor material refers to a mixture of limestone, clay and gypsum burned together under temperatures greater than 1000° C. that may begin to harden instantly or within a few minutes while in contact with water. A non-hydraulic cement precursor material refers to a mixture of lime, gypsum, plasters and oxychloride. A non-hydraulic cement precursor may take longer to harden or may require drying conditions for proper strengthening, but often is more economically feasible. A hydraulic or non-hydraulic cement precursor material may be chosen based on the desired application of the geopolymer cement slurry of the present disclosure. In some embodiments, the cement precursor material may be Portland cement precursor, for example, Class G Portland Cement. Portland cement precursor is a hydraulic cement precursor (cement precursor material that not only hardens by reacting with water but also forms a water-resistant product) produced by pulverizing clinkers, which contain hydraulic calcium silicates and one or more of the forms of calcium sulfate as an inter-ground addition. In other embodiments, the cement precursor material may be Saudi cement precursor, a combination of Portland cement precursor and crystalline silica, also known as quartz.

The cement precursor material may include one or more of calcium hydroxide, silicates, oxides, belite (Ca₂SiO₅), alite (Ca₃SiO₄), tricalcium aluminate (Ca₃Al₂O₆), tetracalcium aluminoferrite (Ca₄Al₂Fe₂O₁₀), brownmilleriate (4CaO.Al₂O₃.Fe₂O₃), gypsum (CaSO₄.2H₂O) sodium oxide, potassium oxide, limestone, lime (calcium oxide), hexavalent chromium, trivalent chromium, calcium aluminate, silica sand, silica flour, hematite, manganese tetroxide, other similar compounds, and combinations of these. The cement precursor material may include Portland cement, siliceous fly ash, calcareous fly ash, slag cement, silica fume, quartz, any known cement precursor material or combinations of any of these. Silica flour is a finely ground crystalline silica with a molecular formula of SiO₂ and with a grain size ranging from 1 to 500 microns, from 10 to 500 microns, from 10 to 100 microns, from 10 to 80 microns, from 10 to 50 microns, from 10 to 20 microns, from 20 to 100 microns, from 20 to 80 microns, from 20 to 50 microns, from 50 to 100 microns, from 50 to 80 microns, or from 80 to 100 microns.

The geopolymer cement slurry may include Saudi Class G cement. Saudi Class G cement may include from 60 to 100 wt. %, from 60 to 99 wt. %, from 60 to 98 wt. %, from 60 to 97 wt. %, from 60 to 96 wt. %, from 60 to 95 wt. %, from 60 to 90 wt. %, from 60 to 80 wt. %, from 60 to 70 wt. %, from 70 to 100 wt. %, from 70 to 99 wt. %, from 70 to 98 wt. %, from 70 to 97 wt. %, from 70 to 96 wt. %, from 70 to 95 wt. %, from 70 to 90 wt. %, from 70 to 80 wt. %, from 80 to 100 wt. %, from 80 to 99 wt. %, from 80 to 98 wt. %, from 80 to 97 wt. %, from 80 to 96 wt. %, from 80 to 95 wt. %, from 80 to 90 wt. %, from 90 to 100 wt. %, from 90 to 99 wt. %, from 90 to 98 wt. %, from 90 to 97 wt. %, from 90 to 96 wt. %, from 90 to 95 wt. %, from 95 to 100 wt. %, from 95 to 99 wt. %, from 95 to 98 wt. %, from 95 to 97 wt. %, from 95 to 96 wt. %, from 96 to 100 wt. %, from 96 to 99 wt. %, from 96 to 98 wt. %, from 96 to 97 wt. %, from 97 to 100 wt. %, from 97 to 99 wt. %, from 97 to 98 wt. %, from 98 to 100 wt. %, from 98 to 99 wt. %, or from 99 to 100 Portland cement. Saudi Class G cement may include less than 40 wt. %, less than 30 wt. %, less than 20 wt. %, less than 10 wt. %, less than 5 wt. %, less than 4 wt. %, less than 3 wt. %, less than 2 wt. %, or less than 1 wt. % crystalline silica, or quartz. Saudi Class G cement may have a pH of greater than 7, of from 8 to 14, of from 10 to 13, of from 11 to 13, of from 12 to 13, or of 12.4. Saudi Class G cement may have a bulk density at 20° C. of from 70 to 120 lb/ft³, of from 80 to 110 lb/ft³, of from 90 to 100 lb/ft³, or of 94 lb/ft³. Saudi Class G cement may have a solubility in water of from 0.1 to 2 grams per 100 milliliters (g/100 ml), of from 0.1 to 1 g/100 ml, of from 0.1 to 0.8 g/100 ml, of from 0.1 to 0.5 g/100 ml, of from 0.2 to 2 g/100 ml, of from 0.2 to 1 g/100 ml, of from 0.2 to 0.8 g/100 ml, of from 0.2 to 0.5 g/100 ml, of from 0.4 to 2 g/100 ml, of from 0.4 to 1 g/100 ml, of from 0.4 to 0.8 g/100 ml, of from 0.4 to 0.5 g/100 ml, of from 0.5 to 2 g/100 ml, of from 0.5 to 1 g/100 ml, of from 0.5 to 0.8 g/100 ml, or of 0.5 g/100 ml.

In some embodiments, the geopolymer cement slurry may contain at least one additive other than Saudi Arabian volcanic ash. The one or more additives may be any additives known to be suitable for geopolymer cement slurries. As non-limiting examples, suitable additives may include accelerators, retarders, extenders, weighting agents, fluid loss control agents, lost circulation control agents, surfactants, antifoaming agents, specialty additives such as elastomers or fibers, and combinations of these.

In some embodiments, the geopolymer cement slurry may contain from 0.1 to 10 wt. % BWOV of the one or more additives based on the total weight of the geopolymer cement slurry. For instance, the geopolymer cement slurry may contain from 0.1 to 8 wt. % BWOV of the one or more additives, from 0.1 to 5 wt. % BWOV of the one or more additives, or from 0.1 to 3 wt. % BWOV of the one or more additives. The geopolymer cement slurry may contain from 1 to 10 wt. % BWOV of the one or more additives, from 1 to 8 wt. % BWOV, from 1 to 5 wt. % BWOV, or from 1 to 3 wt. % BWOV of the one or more additives. In some embodiments, the geopolymer cement slurry may contain from 3 to 5 wt. % BWOV, from 3 to 8 wt. % BWOV, from 3 to 10 wt. % BWOV, or from 5 to 10 wt. % BWOV of the one or more additives.

In some embodiments, the one or more additives may include a dispersant containing one or more anionic groups. For instance, the dispersant may include synthetic sulfonated polymers, lignosulfonates with carboxylate groups, organic acids, hydroxylated sugars, other anionic groups, or combinations of any of these. Without being bound by any particular theory, in some embodiments, the anionic groups on the dispersant may be adsorbed on the surface of the cement particles to impart a negative charge to the geopolymer cement slurry. The electrostatic repulsion of the negatively charged cement particles may allow the geopolymer cement slurry to be dispersed and more fluid-like, improving flowability. This may allow for one or more of turbulence at lesser pump rates, reduction of friction pressure when pumping, reduction of water content, and improvement of the performance of fluid loss additives.

In some embodiments, the one or more additives may alternatively or additionally include a fluid loss additive. In some embodiments, the cement fluid loss additive may include non-ionic cellulose derivatives. In some embodiments, the cement fluid loss additive may be hydroxyethylcellulose (HEC). In other embodiments, the fluid loss additive may be a non-ionic synthetic polymer (for example, polyvinyl alcohol or polyethyleneimine). In some embodiments, the fluid loss additive may include bentonite, which may additionally viscosify the geopolymer cement slurry and may, in some embodiments, cause additional retardation effects.

In some embodiments, the geopolymer cement slurry may contain from 0.1 to 10 wt. % BWOV of one or more fluid loss additives, the one or more dispersants, or both. The geopolymer cement slurry may contain from 0.02 to 90 pound per barrel (lb/bbl) of the fluid loss additives, the one or more dispersants, or both based on the total weight of the geopolymer cement slurry. For instance, the geopolymer cement slurry may contain from 0.1 to 90 lb/bbl, from 0.1 to 75 lb/bbl, from 0.1 to 50 lb/bbl, from 1 to 90 lb/bbl, from 1 to 50 lb/bbl, from 5 to 90 lb/bbl, or from 5 to 50 lb/bbl of the fluid loss additives, the one or more dispersants, or both.

The geopolymer cement slurry may further include resin. As used in this disclosure, a “resin” is a substance of plant or synthetic origin that is typically convertible into polymers, and may be a mixture of organic compounds such as terpenes, an organic compound produced by plants. The viscosity of resin may be greater than 20 cP, measured at a temperature of 120° C. In one embodiment, the resin may have no additional additives. The resin may include at least one of phenol, furan, epoxy, urethane, phenol-formaldehyde, polyester, vinyl ester, and urea aldehyde. The resin may include phenol-formaldehyde. The phenol-formaldehyde resin may include novolac resin or resole resin. Novolac resins are phenol-formaldehyde resins with a formaldehyde to phenol molar ratio of less than 1, where the phenol units are mainly linked by methylene or ether groups, or both. The novolac has a glass transition temperature greater than 250° F., 300° F., 350° F., 390° F., 400° F., 450° F., or 500° F. Novolac resins are stable, meaning that they do not react and do retain their polymer properties at temperatures of up to 300° F., 400° F., 425° F., 450° F., 475° F., 500° F., 550° F., or 600° F. Resole resins are phenol-formaldehyde resins with a formaldehyde to phenol molar ratio of more than 1, where the phenol units are mainly linked by methylene or ether groups, or both. This can harden without the addition of a crosslinking agent due to abundance of methylene to bridge the phenol groups. In embodiments, the resin may include bisphenol-A-epichlorohydrin epoxy; 2,3-epoxypropyl-o-tolyl ether; alkyl glycidyl ether; 1,6-hexanediol diglycidyl ether; butyl glycidyl ether; cyclohexanedimethanol; cyclohexanedimethanol diclydicyl ether; or combinations of these. The resin may increase bonding between the geopolymer cement slurry and the casing or annulus. The geopolymer cement slurry may include from 1 to 60 wt. %, from 1 to 50 wt. %, from 1 to 45 wt. %, from 1 to 40 wt. %, from 1 to 35 wt. %, from 1 to 30 wt. %, from 1 to 25 wt. %, from 1 to 20 wt. %, from 1 to 10 wt. %, from 10 to 60 wt. %, from 10 to 50 wt. %, from 10 to 45 wt. %, from 10 to 40 wt. %, from 10 to 35 wt. %, from 10 to 30 wt. %, from 10 to 25 wt. %, from 10 to 20 wt. %, from 20 to 60 wt. %, from 20 to 50 wt. %, from 20 to 45 wt. %, from 20 to 40 wt. %, from 20 to 35 wt. %, from 20 to 30 wt. %, from 20 to 25 wt. %, from 25 to 60 wt. %, from 25 to 50 wt. %, from 25 to 45 wt. %, from 25 to 40 wt. %, from 25 to 35 wt. %, from 25 to 30 wt. %, from 30 to 60 wt. %, from 30 to 50 wt. %, from 30 to 45 wt. %, from 30 to 40 wt. %, from 30 to 35 wt. %, from 35 to 60 wt. %, from 35 to 50 wt. %, from 35 to 45 wt. %, from 35 to 40 wt. %, from 40 to 60 wt. %, from 40 to 50 wt. %, from 40 to 45 wt. %, from 50 to 60 wt. %, or about 35 wt. % BWOV resin.

The resin might contain 50 wt. % to 97 wt. % epoxy resin, the epoxy resin comprising at least one of 2,3-epoxypropyl o-tolyl ether, alkyl glycidyl ethers having from 12 to 14 carbon atoms, bisphenol-A-epichlorohydrin epoxy resin, bisphenol-F-based epoxy resins, aliphatic epoxy resins, or a compound having formula (I):

(OC₂H₃)—CH₂—O—R¹—O—CH₂—(C₂H₃O)  (I)

where R¹ is a linear or branched hydrocarbyl having from 4 to 24 carbon atoms (such as from 4 to 20, from 4 to 16, from 4 to 12, from 4 to 8, from 6 to 24, from 6 to 20, from 6 to 16, or from 6 to 12 carbon atoms) and where the epoxy resin has an epoxy equivalent weight of from 170 to 350 epoxy equivalents per gram. In some embodiments, R¹ may be an alkyl group. The composition may also include from 2 wt. % to 30 wt. % curing agent. The resin may include at least one epoxy resin and at least one curing agent. For example, in one embodiment, the epoxy resin may include 1,6-hexanediol diglycidyl ether, which has formula (II):

(OC₂H₃)—CH₂—O—C₆H₁₂—O—CH₂—(C₂H₃O)  (II)

In some embodiments, the epoxy resin may include at least one of 1,6-hexanediol diclycidyl ether, alkyl glycidyl ethers having from 12 to 14 carbon atoms, 2,3-epoxypropyl o-tolyl ether, or bisphenol-A-epichlorohydrin epoxy resin. Alternatively, in other embodiments, the epoxy resin may include at least one of 1,6-hexanediol diclycidyl ether, alkyl glycidyl ethers having from 12 to 14 carbon atoms, or 2,3-epoxypropyl o-tolyl ether.

The epoxy resin may have an epoxy value of from 4.5 epoxy equivalents per kilogram of the epoxy resin to 5.5 epoxy equivalents per kilogram of the epoxy resin. The epoxy equivalent weight of an epoxy resin is the weight of the epoxy resin in grams that contains one equivalent weight of epoxy. The epoxy equivalent weight of the epoxy resin is equal to the molecular weight of the epoxy resin divided by the average number of epoxy groups in the epoxy resin. The epoxy resins may have an epoxy equivalent weight of from 170 to 350 grams of resin per epoxy equivalent (g/eq). The epoxy value and epoxy equivalent weight of an epoxy resin may be determined according to ASTM-D1652. Other methods of determining the epoxy value and epoxy equivalent weight of the epoxy resin may also be used to determine the epoxy value or epoxy equivalent weight of the epoxy resin.

In some embodiments, the epoxy resin may be modified with a reactive diluent. The type and amount of reactive diluent may influence the viscosity, flexibility, hardness, chemical resistance, mechanical properties, plasticizing effect, reactivity, crosslinking density, or other properties of the epoxy resin. In some embodiments, the reactive diluent may be added to the epoxy resin to change the viscosity of the epoxy resin, such as to reduce the viscosity of the epoxy resin. In other embodiments, the reactive diluents may be added to improve at least one of the adhesion, the flexibility, and the solvent resistance of the epoxy resin. The reactive diluent can be a non-functional, mono-functional, di-functional, or multi-functional reactive diluent. For example, a non-functional reactive diluent does not have an epoxide functional group. As used in relation to reactive diluents, the term “functional” refers to the reactive diluent having at least one epoxide functional group. Therefore, a functional reactive diluent may have one, two, three, or more than three epoxide functional groups.

The term “non-functional”, as used in relation to reactive diluents, refers to a reactive diluent that does not have at least one epoxide functional group. Thus, a non-functional reactive diluent does not have at least one epoxide functional group, but still participates in at least one chemical reaction during reaction of the epoxide resin. The term “non-reactive diluent” refers to a diluent that does not participate in a chemical reaction during reaction of the epoxy resin. Examples of reactive and non-reactive diluents may include, but are not limited to, propylene glycol diglycidyl ether, butanediol diglycidyl ether, cardanol glycidyl ether derivatives, propanetriol triglycidyl ether, aliphatic monoglycidyl ethers of C13-C15 alcohols, or combinations of functional or non-functional reactive diluents and non-reactive diluents. In some embodiments, the epoxy resin may include a reactive diluent having the formula (III):

R₂—O—CH₂—(C₂H₃O)  (III)

where R₂ is a hydrocarbyl having from 12 to 14 carbon atoms. R₂ may be linear, branched, or cyclic. In some embodiments, R₂ may be an alkyl group.

In some embodiments, the epoxy resin may include an amount of reactive diluent that reduces the viscosity of the epoxy resin. In other embodiments, the epoxy resin may include an amount of reactive diluent that modifies one or more of the adhesion, the flexibility, or the solvent resistance of the epoxy resin. In some embodiments, the epoxy resin may include from 1 wt. % to 30 wt. % reactive diluent based on the total weight of the epoxy resin portion of the epoxy resin system. As used in this disclosure, the term “epoxy resin portion” refers to the constituents of the epoxy resin system that do not include the curing agent, weighting agents, or other additives, such as accelerators or retarders. The epoxy resin portion includes the epoxy resins and any added reactive or non-reactive diluent. In other embodiments, the epoxy resin may include from 1 wt. % to 20 wt. %, from 1 wt. % to 16 wt. %, from 1 wt. % to 14 wt. %, from 1 wt. % to 12 wt. %, from 5 wt. % to 30 wt. %, from 5 wt. % to 20 wt. %, from 5 wt. % to 16 wt. %, from 5 wt. % to 14 wt. %, from 5 wt. % to 12 wt. %, from 10 wt. % to 30 wt. %, from 10 wt. % to 20 wt. %, from 10 wt. % to 16 wt. %, from 10 wt. % to 14 wt. %, from 12 wt. % to 30 wt. %, from 12 wt. % to 20 wt. %, from 12 wt. % to 16 wt. %, from 14 wt. % to 30 wt. %, from 14 wt. % to 20 wt. %, or from 14 wt. % to 16 wt. % reactive diluent based on the total weight of the epoxy resin portion of the epoxy system.

In some embodiments, the epoxy resin may include bisphenol-A-(epichlorohydrin) epoxy resin with oxirane mono [(C12-C14)-alkyloxy)methyl] derivatives. The bisphenol-A-epichlorohydrin epoxy resin is an epoxy resin made by reaction of bisphenol-A and epichlorohydrin. The bisphenol-A-(epichlorohydrin) epoxy resin may then be modified with the reactive diluent oxirane mono[(C12-C14)-alkyloxy) methyl] derivatives to reduce the viscosity of the resin and improve the adhesion, flexibility, and solvent resistance of the final resin.

In some embodiments, the epoxy resin may include from 80 wt. % to 90 wt. %, from 80 wt. % to 88 wt. %, from 80 wt. % to 86 wt. %, from 80 wt. % to 84 wt. %, from 82 wt. % to 90 wt. %, from 82 wt. % to 88 wt. %, from 82 wt. % to 86 wt. %, from 82 wt. % to 84 wt. %, from 84 wt. % to 90 wt. %, from 84 wt. % to 88 wt. %, or from 84 wt. % to 86 wt. % of the bisphenyl-A-epichlorohydrin epoxy resin based on the total weight of the epoxy resin. In some embodiments, the epoxy resin may include from 10 wt. % to 20 wt. %, from 10 wt. % to 18 wt. %, from 10 wt. % to 16 wt. %, from 10 wt. % to 14 wt. %, from 12 wt. % to 20 wt. %, from 12 wt. % to 18 wt. %, from 12 wt. % to 16 wt. %, from 12 wt. % to 14 wt. %, from 14 wt. % to 20 wt. %, from 14 wt. % to 18 wt. %, or from 14 wt. % to 16 wt. % oxirane mono[(C12-C14)-alkyloxy)methyl] derivatives based on the total weight of the epoxy resin portion of the epoxy resin system.

In some embodiments, the epoxy resin comprising the bisphenol-A-(epichlorohydrin) epoxy resin with the reactive diluent oxirane mono[(C₁₂-C₁₄)-alkyloxy) methyl] derivatives may have an epoxy value of from 4.76 epoxy equivalents per kilogram of epoxy resin to 5.26 epoxy equivalents per kilogram of epoxy resin. The epoxy resin comprising the bisphenol-A-(epichlorohydrin) epoxy resin with the reactive diluent oxirane mono[(C₁₂-C₁₄)-alkyloxy) methyl] derivatives may have an epoxy equivalent weight of 190 g/eq to 210 g/eq and a dynamic viscosity of from 600 millipascal seconds (mPa·s) to 1200 mPa·s, or 600 mPa·s to 900 mPa·s.

In some embodiments, the epoxy resin may include 2,3-epoxypropyl-o-tolyl ether, which may have an epoxy equivalent weight of from 170 g/eq to 190 g/eq and exhibit a dynamic viscosity of from 7 mPa·s to 10 mPa·s. In other embodiments, the epoxy resin may include alkyl glycidyl ethers having from 12 to 14 carbon atoms, which may have an epoxy equivalent weight of from 270 g/eq to 305 g/eq and may exhibit a dynamic viscosity of from 5 mPa·s to 12 mPa·s. In some embodiments, the epoxy resin may include 1,6-hexanediol diclycidyl ether, which may have an epoxy equivalent weight of from 150 g/eq to 170 g/eq and may exhibit a dynamic viscosity of from 20 mPa·s to 30 mPa·s.

In some embodiments, the epoxy resin system may include a plurality of epoxy resins. For example, in some embodiments, the epoxy resin system may include a combination of two or more of bisphenol-A-epichlorohydrin epoxy resin, 2,3-epoxypropyl-o-tolyl ether, C₁₂-C₁₄ alkyl glycidyl ether, or 1,6-hexanediol diglycidyl ether epoxy resin. In one embodiment, the epoxy resin may include a mixture of 1,6-hexanediol diglycidyl ether epoxy resin and bisphenol-A-epichlorohydrin epoxy resin with the reactive diluent oxirane mono [(C₁₂-C₁₄)-alkyloxy)methyl] derivatives.

As previously discussed in this disclosure, the epoxy resin system includes a curing agent to cure the epoxy resin. The curing agent may include at least one of an amine, polyamine, amine adduct, polyamine adduct, alkanolamine, amide, polyamide, polyamide adduct, polyamide imidazoline, polyaminoamides, phenalkamine, or combinations of these. Amines or polyamine curing agents may include, but are not limited to, aliphatic amines, cycloaliphatic amines, modified cycloaliphatic amines such as cycloaliphatic amines modified by polyacrylic acid, aliphatic polyamines, cycloaliphatic polyamines, modified polyamines such as polyamines modified by polyacrylic acid, or amine adducts such as cycloaliphatic amine adducts or polyamine adducts.

In some embodiments, the curing agent may include at least one of trimethyl hexamethylene diamine (TMD), diethylenetriamine (DETA), triethylenetetramine (TETA), meta-xylenediamine (MXDA), aminoethylpiperazine (AEP), tetraethylenepentamine (TEPA), polyetheramine, isophoronediamine (IPDA), beta-hydroxyalkyl amide (HAA), or combinations of these. In other embodiments, the curing agent may include at least one of DETA, TETA, TEPA, IPDA, or combinations of these. In some embodiments, the epoxy resin system may include a plurality of curing agents.

The curing agent may be an amine curing agent having an amine value that enables the amine curing agent to fully cure the epoxy resin system. The amine value of a curing agent gives the active hydrogen (NH) content of an amine curing agent. The amine value is expressed as the weight in milligrams of potassium hydroxide (KOH) needed to neutralize the NH in 1 gram of the amine curing agent. In some embodiments, the curing agent may have an amine value of from 250 milligrams of KOH per gram (mg KOH/g) to 1700 mg KOH/g, from 250 mg KOH/g to 1650 mg KOH/g, from 250 mg KOH/g to 1600 mg KOH/g, from 450 mg KOH/g to 1700 mg KOH/g, from 450 mg KOH/g to 1650 mg KOH/g, from 450 mg KOH/g to 1600 mg KOH/g, from 650 mg KOH/g to 1700 mg KOH/g, from 650 mg KOH/g to 1650 mg KOH/g, or from 650 mg KOH/g to 1600 mg KOH/g. The amine value may be determined by titrating a solution of the curing agent with a dilute acid, such as a 1 N solution of hydrogen chloride (HCl). The amine value may then be calculated from the amount of HCl needed to neutralize the amine in the solution according to Equation 2:

$\begin{matrix} \frac{V_{HCl}*N_{HCl}*MW_{KOH}}{W} & {{Equation}\mspace{14mu} 2} \end{matrix}$

where V_(HCl) is the volume in milliliters of HCl needed to neutralize the amine, N_(HCl) is the normality of HCl used to titrate the amine, MW_(KOH) is the molecular weight of KOH in grams per mole, and W is the weight in grams of the curing agent sample titrated. The amine number of the known pure amine curing agent may be calculated from Equation 3:

$\begin{matrix} \frac{1000*MW_{KOH}}{MW_{{curing}\mspace{11mu}{agent}}} & {{Equation}\mspace{14mu} 3} \end{matrix}$

where MW_(KOH) is the molecular weight of KOH in grams per mole, and MW_(curing agent) is the molecular weight of the curing agent in grams per mole.

The amine curing agent may have an amine hydrogen equivalent weight (AHEW) that enables the amine curing agent to fully cure the epoxy resin system. The AHEW of an amine curing agent refers to the grams of the amine curing agent containing 1 equivalent of amine. The AHEW of an amine curing agent may be calculated by dividing the molecular weight of the amine curing agent in grams per mole by the number of active hydrogens per molecule. In some embodiments, the curing agent may be an amine curing agent having an AHEW of from 20 grams (g) to 120 g, from 20 g to 115 g, from 20 g to 110 g, from 20 g to 100 g, from 40 g to 120 g, from 40 g to 115 g, from 40 g to 110 g, from 40 g to 110 g, from 60 g to 120 g, from 60 g to 115 g, or from 60 g to 110 g determined according to the methods previously described in this disclosure.

The curing time of the resin may be inversely proportional to the amount of curing agent in the resin. For example, increasing the amount of the curing agent in the resin may result in a decrease in the curing time of the resin. In some embodiments, the resin may include an amount of curing agent capable of curing the epoxy resin in the resin to a semi-solid state in a cure time of from 4 hours to 12 hours. As used in this disclosure, the term “semi-solid” refers to a state of the compositions that is between a liquid and a solid in which the composition exhibits high elasticity and flexibility. In the semi-solid state, the resin may be easily deformed but may return to shape upon releasing the deforming force. The resins cured to a semi-solid or solid state are capable of sealing the annulus of the wellbore.

In some embodiments, the geopolymer cement slurry may include an amount of the curing agent capable of curing the resin to a semi-solid state within a cure time of from 4 hours to 9 hours. In some embodiments, the geopolymer cement slurry may include from 0.1 wt. % to 20 wt. % curing agent based on the total weight of the resin before curing. In other embodiments, the geopolymer cement slurry may have from 0.1 wt. % to 15 wt. %, from 0.1 wt. % to 10 wt. %, from 0.1 wt. % to 5 wt. %, from 0.5 wt. % to 20 wt. %, from 0.5 wt. % to 15 wt. %, from 0.5 wt. % to 10 wt. %, from 0.5 wt. % to 5 wt. %, from 1 wt. % to 20 wt. %, from 1 wt. % to 15 wt. %, from 1 wt. % to 10 wt. %, from 1 wt. % to 5 wt. %, from 5 wt. % to 20 wt. %, from 5 wt. % to 15 wt. %, from 5 wt. % to 10 wt. %, or from 10 wt. % to 20 wt. % curing agent based on the total weight of the resin before curing.

The epoxy resin system may also include one or more additives to modify the speed of the reaction between the epoxy resin and the curing agent or modify other properties of the resin system, such as viscosity, yield point (YP), or other rheological properties. For example, in some embodiments, the epoxy resin system may include an accelerator or a retarder to speed up or slow down the reaction between the epoxy resin and the curing agent. Accelerators may include, but are not limited to, alcohols, phenols, aminoalcohols, or amines. Examples of accelerators may include, but are not limited to benzyl alcohol, mono-nonylphenol, triethanolamine (TEA), amino-n-propyl diethanolamine, n,n-dimethyldipropylenetramine, or combinations of these. Examples of retarders may include lignin, gums, starches, lignosulphonate derivatives, or combinations of these.

In some embodiments, the geopolymer cement slurry may include an amount of the accelerator capable of decreasing the cure time of the geopolymer cement slurry from greater than 12 hours to a cure time in a range of from 1 hour to 12 hours. In some embodiments, the geopolymer cement slurry may include from 0.01 wt. % to 10 wt. % accelerator based on the total weight of the geopolymer cement slurry prior to curing. In other embodiments, the geopolymer cement slurry may include from 0.01 wt. % to 5 wt. %, from 0.01 wt. % to 3 wt. %, from 0.01 wt. % to 1 wt. %, from 0.1 wt. % to 10 wt. %, from 0.1 wt. % to 5 wt. %, from 0.1 wt. % to 3 wt. %, from 0.1 wt. % to 1 wt. %, from 1 wt. % to 10 wt. %, from 1 wt. % to 5 wt. %, or from 1 wt. % to 3 wt. % accelerator based on the total weight of the geopolymer cement slurry prior to curing.

The geopolymer cement slurrys may include one or more weighting materials. The weighting materials may be particulate solids having a specific gravity (SG) that increases the density of the geopolymer cement slurry. The weighting material may be added to the geopolymer cement slurry to increase the density of the final cured resin to increase the hydrostatic pressure exerted by the geopolymer cement slurry on the wellbore wall or the interior surface of the outer tubular string. The final density of the cured resin may depend on the geology of the subterranean formation in the zone being sealed. For example, in some embodiments, the subterranean formation may require a geopolymer cement slurry having a greater density to support the wellbore and prevent flow of fluids from the subterranean formation into the wellbore during curing of the geopolymer cement slurry.

The weighting material may have a specific gravity (SG) of from 2 to 6. Examples of weighting materials may include, but are not limited to, sand, barite (barium sulfate), hematite, calcium carbonate, siderite, ilmenite, silica sand, manganese oxide (MnO), hausmanite (manganese tetraoxide (Mn₃O₄), zinc oxide, zirconium oxide, iron oxide, or any combination of these weighting materials. In some embodiments, geopolymer cement slurry may include manganese tetraoxide.

The geopolymer cement slurry may include an amount of weighting material that increases the density of the geopolymer cement slurry. In some embodiments, the sealing composition may include from 0.1 wt. % to 40 wt. % weighting material based on the total weight of the geopolymer cement slurry prior to curing. For example, in some embodiments, the geopolymer cement slurry may include from 0.1 wt. % to 30 wt. %, from 0.1 wt. % to 20 wt. %, from 0.1 wt. % to 10 wt. %, from 1 wt. % to 40 wt. %, from 1 wt. % to 30 wt. %, from 1 wt. % to 20 wt. %, from 1 wt. % to 10 wt. %, from 5 wt. % to 40 wt. %, from 5 wt. % to 30 wt. %, from 5 wt. % to 20 wt. %, from 5 wt. % to 10 wt. %, from 10 wt. % to 40 wt. %, from 10 wt. % to 30 wt. %, from 10 wt. % to 20 wt. %, or from 20 wt. % to 40 wt. % weighting material based on the total weight of the geopolymer cement slurry before curing.

The geopolymer cement slurry may have a thickening time at 100° F. of greater than 1, 2, 5, 10, or 12 hours. A thickening time test is used to simulate pumping conditions in order to determine a length of time before the cement becomes difficult or impossible to pump. The most common method to determine thickening time is via a pressurized consistometer. This device allows pressure and temperature to be applied to a geopolymer cement slurry while it is being stirred (typically at 150 rpm). A resistor arm on a potentiometer indicates resistance to the paddle turning as the cement sets. The apparatus is calibrated to a standard output in Bearden Consistency units. The device is fully automated and can simulate squeeze schedules and/or batch mixing, etc.

The geopolymer cement slurry may have a density of from 100 to 140 lb/ft³. In other embodiments, the geopolymer cement slurry may have a density of from 100 to 130 lb/ft³, from 100 to 120 lb/ft³, from 100 to 115 lb/ft³, from 100 to 110 lb/ft³, from 100 to 105 lb/ft³, from 105 to 140 lb/ft³, from 105 to 130 lb/ft³, from 105 to 120 lb/ft³, from 105 to 115 lb/ft³, from 105 to 110 lb/ft³, from 110 to 140 lb/ft³, from 110 to 130 lb/ft³, from 110 to 120 lb/ft³, from 110 to 115 lb/ft³, from 115 to 140 lb/ft³, from 115 to 130 lb/ft³, from 115 to 120 lb/ft³, from 120 to 140 lb/ft³, from 120 to 130 lb/ft³, or from 130 to 140 lb/ft³.

The viscosity of the geopolymer cement slurry compositions may be measured using a standard oilfield viscometer, such as a FANN® Model 35 viscometer manufactured by Fann Instrument Company for example, according to test methods provided in the API Recommended Practice For Field Testing Water-Based Geopolymer cement slurries (RP 13B-1/ISO 10414-1:2002). The viscometer reports shear stress readings at various shear rates. The shear stress readings are reported in units of pounds of force per 100 square feet (lbf/100 ft²). The shear rate is measured in rpm. The viscometer may report shear stress readings at shear rates of at least one of 600 rpm, 300 rpm, 200 rpm, 100 rpm, 6 rpm, or 3 rpm. These shear stress readings may be used to determine the viscosity of the geopolymer cement slurry at any of the shear rates, using Equation 4, assuming a viscometer with an R1 rotor sleeve, B1 bob, and F1 torsion spring:

$\begin{matrix} {\mu = {\frac{300}{N}\theta_{N}}} & {{Equation}\mspace{14mu} 4} \end{matrix}$

Where

μ=viscosity, (cp) N=viscometer speed, shear rate (rpm) θ_(N)=viscometer reading, shear stress (lbf/100 ft²)

The rheology of geopolymer cement slurry compositions may be modeled based on Bingham plastic flow behavior. In particular, the geopolymer cement slurry composition having Saudi Arabian volcanic ash behaves as a rigid body at lesser shear stress but flows as a viscous fluid at greater shear stress. The rheological behavior of the geopolymer cement slurry composition may be determined by measuring the shear stress on the geopolymer cement slurry composition at different shear rates, which may be accomplished by measuring the shear stress and/or shear rate on the geopolymer cement slurry composition using a FANN® Model 35 viscometer operated at 3 rpm, 6 rpm, 100 rpm, 200 rpm, 300 rpm, or 600 rpm, for example. A Bingham plastic fluid may be modeled by Equation 5.

τ=(PV){dot over (γ)}+4.79YP  Equation 5

Where

τ=shear stress, (dynes per square centimeter (dyne/cm²)) PV=plastic viscosity, (cP) {dot over (γ)}=shear rate, (s⁻¹) YP=yield point, (lbf/100 ft²)

The rheology of the geopolymer cement slurry composition may be evaluated from the plastic viscosity (PV) and the yield point (YP), which are parameters from the Bingham plastic rheology model. The PV is related to the resistance of the geopolymer cement slurry composition to flow due to mechanical interaction between the solids of the geopolymer cement slurry composition and represents the viscosity of the geopolymer cement slurry composition extrapolated to infinite shear rate. In other words, the PV is the slope of the shear stress versus shear rate curve of the Bingham plastic model. The PV reflects the type and concentration of the solids in the geopolymer cement slurry composition, and a lesser PV is preferred. The PV of the geopolymer cement slurry composition may be estimated by measuring the shear stress of the geopolymer cement slurry using a FANN® Model 35 viscometer at shear rates of 300 rpm and 600 rpm and subtracting the 300 rpm shear stress measurement from the 600 rpm shear stress measurement according to Equation 6.

PV=θ ₆₀₀−θ₃₀₀  Equation 6

Where

PV=plastic viscosity, (cP) θ₆₀₀=shear stress viscometer reading at 600 rpm, (lbf/100 ft²) θ₃₀₀=shear stress viscometer reading at 300 rpm, (lbf/100 ft²)

When the shear stress measurement at 600 rpm is not available, the plastic viscosity may be calculated by determining the difference between any two shear stress measurements, dividing the difference by the difference of the shear rates that the two shear stresses were measured at, and multiplying that factor by 300. This formula is provided in Equation 7.

$\begin{matrix} {{PV} = {\frac{300}{N_{2} - N_{1}}\left( {\theta_{N_{2}} - \theta_{N_{1}}} \right)}} & {{Equation}\mspace{14mu} 7} \end{matrix}$

Where

PV=plastic viscosity, (cP) N=viscometer speed, shear rate (rpm) θ_(N)=shear stress viscometer reading at N rpm, (lbf/100 ft²)

The YP represents the shear stress less than which the geopolymer cement slurry composition behaves as a rigid body and greater than which the geopolymer cement slurry composition flows as a viscous fluid. In other words, the YP represents the amount of stress required to move the geopolymer cement slurry composition from a static condition. The yield point is the resistance of initial flow of a fluid, or the stress required in order to move the fluid. It can be simply stated that the yield point is the attractive force among colloidal particles in geopolymer cement slurry. The YP of a geopolymer cement slurry composition is correlated with the capacity of the geopolymer cement slurry composition to carry rock cuttings through the annulus, which in simplified terms indicates the geopolymer cement slurry composition's hole-cleaning ability. The determination of yield points in geopolymer cement slurries is important in the overall description of slurry flow properties. Yield point affects both the start-up pressure after a temporary shut-down and the void filling properties of cements during cementing operations. YP of equal to or greater than 15 lbf/100 ft² is considered acceptable for drilling. The YP is determined by extrapolating the Bingham plastic rheology model to a shear rate of zero. In other words, the PV is the y-intercept of the shear stress v. shear rate curve of the Bingham plastic model. The YP of the geopolymer cement slurry composition may be estimated from the PV from Equation 7 by subtracting the PV from Equation 7 from the shear stress of the geopolymer cement slurry measured at 300 rpm according to Equation 8.

YP=θ ₃₀₀ −PV  Equation 8

The YP is expressed as a force per area, such as in field units of lbf/100 ft², for example. The YP may be converted to SI units of dyne/cm², as 1 lbf/100 ft²=4.79 dyne/cm². The methods for measuring and determining PV and YP for the geopolymer cement slurry compositions having Saudi Arabian volcanic ash are consistent with methods conventionally used for geopolymer cement slurries in general.

The geopolymer cement slurry may have a plastic viscosity of from 50 to 350 cP. In other embodiments, the geopolymer cement slurry may have a plastic viscosity of from 50 to 350 cP, from 50 to 300 cP, from 50 to 200 cP, from 50 to 150 cP, from 50 to 125 cP, from 50 to 100 cP, from 50 to 80 cP, from 50 to 60 cP, from 60 to 350 cP, from 60 to 300 cP, from 60 to 200 cP, from 60 to 150 cP, from 60 to 125 cP, from 60 to 100 cP, from 60 to 80 cP, from 80 to 350 cP, from 80 to 300 cP, from 80 to 200 cP, from 80 to 150 cP, from 80 to 125 cP, from 80 to 100 cP, from 100 to 350 cP, from 100 to 300 cP, from 100 to 200 cP, from 100 to 150 cP, from 100 to 125 cP, from 100 to 100 cP, from 100 to 80 cP, from 125 to 350 cP, from 125 to 300 cP, from 125 to 200 cP, from 125 to 150 cP, from 150 to 350 cP, from 150 to 300 cP, from 150 to 200 cP, from 200 to 300 cP, from 200 to 350 cP, or from 300 to 350 cP.

The geopolymer cement slurry of the present disclosure may have a yield point of from 5 to 70 lbf/100 ft², from 5 to 60 lbf/100 ft², from 5 to 55 lbf/100 ft², from 5 to 40 lbf/100 ft², from 5 to 30 lbf/100 ft², from 5 to 25 lbf/100 ft², from 5 to 20 lbf/100 ft², from 5 to 15 lbf/100 ft², from 5 to 10 lbf/100 ft², from 10 to 70 lbf/100 ft², from 10 to 60 lbf/100 ft², from 10 to 55 lbf/100 ft², from 10 to 40 lbf/100 ft², from 10 to 30 lbf/100 ft², from 10 to 25 lbf/100 ft², from 10 to 20 lbf/100 ft², from 10 to 15 lbf/100 ft², from 15 to 70 lbf/100 ft², from 15 to 60 lbf/100 ft², from 15 to 55 lbf/100 ft², from 15 to 40 lbf/100 ft², from 15 to 30 lbf/100 ft², from 15 to 25 lbf/100 ft², from 15 to 20 lbf/100 ft², from 20 to 70 lbf/100 ft², from 20 to 60 lbf/100 ft², from 20 to 55 lbf/100 ft², from 20 to 40 lbf/100 ft², from 20 to 30 lbf/100 ft², from 20 to 25 lbf/100 ft², from 25 to 70 lbf/100 ft², from 25 to 60 lbf/100 ft², from 25 to 55 lbf/100 ft², from 25 to 40 lbf/100 ft², from 25 to 30 lbf/100 ft², from 30 to 70 lbf/100 ft², from 30 to 60 lbf/100 ft², from 30 to 55 lbf/100 ft², from 30 to 40 lbf/100 ft², from 40 to 70 lbf/100 ft², from 40 to 60 lbf/100 ft², from 40 to 55 lbf/100 ft², from 55 to 70 lbf/100 ft², from 55 to 60 lbf/100 ft², or from 60 to 70 lbf/100 ft².

The gel strength of a geopolymer cement slurry refers to the shear stress of the geopolymer cement slurry composition measured at a low shear rate (such as 3 rpm or 6 rpm) following a defined period of time during which the geopolymer cement slurry composition is maintained in a static state. The shear stress of the geopolymer cement slurry composition at low shear rate may be measured using a standard oilfield viscometer, such as a FANN® Model 35 viscometer operated at low rpms, such as at 3 rpm or 6 rpm, according to the test methods described in API Recommended Practice For Field Testing Water-Based Geopolymer cement slurries (RP 13B-1/ISO 10414-1:2002) published August 2014 and incorporated by reference into this disclosure in its entirety. To measure the gel strength, the geopolymer cement slurry composition is first stirred by contacting the geopolymer cement slurry composition with the spindle of the viscometer and operating the viscometer at 600 rotations per minute (rpm). The viscometer is then turned off for period of time (time period). For a 10-second gel strength, the time period is 10 seconds, and for a 10 minute gel strength, the time period is 10 minutes. It should be understood that other time periods for measuring gel strength may be used as reference times for measurements of gel strength. During the time period, the geopolymer cement slurry composition comes to rest in a static state. Upon expiration of the time period, the viscometer is turned back on at a low speed, such as 3 rpm for example, to generate a low shear rate. The viscometer reading is then taken. The gel strength of the geopolymer cement slurry composition is reported in units of lbf/100 ft².

The geopolymer cement slurry described in this disclosure may have a 10-second gel strength of from 5 to 50 lbf/100 ft², from 5 to 40 lbf/100 ft², from 5 to 35 lbf/100 ft², from 5 to 30 lbf/100 ft², from 5 to 25 lbf/100 ft², from 5 to 20 lbf/100 ft², from 5 to 15 lbf/100 ft², from 5 to 10 lbf/100 ft², from 10 to 50 lbf/100 ft², from 10 to 40 lbf/100 ft², from 10 to 35 lbf/100 ft², from 10 to 30 lbf/100 ft², from 10 to 25 lbf/100 ft², from 10 to 20 lbf/100 ft², from 10 to 15 lbf/100 ft², from 15 to 50 lbf/100 ft², from 15 to 40 lbf/100 ft², from 15 to 35 lbf/100 ft², from 15 to 30 lbf/100 ft², from 15 to 25 lbf/100 ft², from 15 to 20 lbf/100 ft², from 20 to 50 lbf/100 ft², from 20 to 40 lbf/100 ft², from 20 to 35 lbf/100 ft², from 20 to 30 lbf/100 ft², from 20 to 25 lbf/100 ft², from 25 to 50 lbf/100 ft², from 25 to 40 lbf/100 ft², from 25 to 35 lbf/100 ft², from 25 to 30 lbf/100 ft², from 30 to 50 lbf/100 ft², from 30 to 40 lbf/100 ft², from 30 to 35 lbf/100 ft², from 35 to 50 lbf/100 ft², from 35 to 40 lbf/100 ft², or from 40 to 50 lbf/100 ft². The 10-second gel strength of the geopolymer cement slurry composition having Saudi Arabian volcanic ash may be compared to a 10-second gel strength of a comparative geopolymer cement slurry without Saudi Arabian volcanic ash. The 10-second gel strength of the geopolymer cement slurry composition having Saudi Arabian volcanic ash may be less than or equal to 90% of the 10-second gel strength of the comparative geopolymer cement slurry, or less than or equal to 80% of the 10-second gel strength of the comparative geopolymer cement slurry, or less than or equal to 70% of the 10-second gel strength of the comparative geopolymer cement slurry.

The geopolymer cement slurry may have a 10 minute gel strength of from 10 to 60 lbf/100 ft², from 10 to 50 lbf/100 ft², from 10 to 45 lbf/100 ft², from 10 to 40 lbf/100 ft², from 10 to 30 lbf/100 ft², from 10 to 25 lbf/100 ft², from 10 to 20 lbf/100 ft², from 10 to 15 lbf/100 ft², from 15 to 60 lbf/100 ft², from 15 to 50 lbf/100 ft², from 15 to 45 lbf/100 ft², from 15 to 40 lbf/100 ft², from 15 to 30 lbf/100 ft², from 15 to 25 lbf/100 ft², from 15 to 20 lbf/100 ft², from 20 to 60 lbf/100 ft², from 20 to 50 lbf/100 ft², from 20 to 45 lbf/100 ft², from 20 to 40 lbf/100 ft², from 20 to 30 lbf/100 ft², from 20 to 25 lbf/100 ft², from 25 to 60 lbf/100 ft², from 25 to 50 lbf/100 ft², from 25 to 45 lbf/100 ft², from 25 to 40 lbf/100 ft², from 25 to 30 lbf/100 ft², from 30 to 60 lbf/100 ft², from 30 to 50 lbf/100 ft², from 30 to 45 lbf/100 ft², from 30 to 40 lbf/100 ft², from 35 to 60 lbf/100 ft², from 35 to 50 lbf/100 ft², from 35 to 45 lbf/100 ft², from 40 to 60 lbf/100 ft², from 40 to 50 lbf/100 ft², from 40 to 45 lbf/100 ft², from 45 to 60 lbf/100 ft², from 45 to 50 lbf/100 ft², or from 50 to 60 lbf/100 ft². The 10-minute gel strength of the geopolymer cement slurry composition having Saudi Arabian volcanic ash may be compared to a 10-minute gel strength of a comparative geopolymer cement slurry without Saudi Arabian volcanic ash. The 10-minute gel strength of the geopolymer cement slurry composition having Saudi Arabian volcanic ash may be less than or equal to 90% of the 10-minute gel strength of the comparative geopolymer cement slurry, or less than or equal to 80% of the 10-minute gel strength of the comparative geopolymer cement slurry, or less than or equal to 70% of the 10-minute gel strength of the comparative geopolymer cement slurry.

Further embodiments of the present disclosure relate to methods of using the geopolymer cement slurries previously described. In some embodiments, the method may include pumping the geopolymer cement slurry into a location to be cemented and curing the geopolymer cement slurry by allowing the aqueous solution and the Saudi Arabian volcanic ash to react. The location to be cemented may, for instance, be a well, a wellbore, an annulus, or other such locations.

Cementing is performed when the geopolymer cement slurry is deployed into the well via pumps, displacing the drilling fluids still located within the well, and replacing them with cement. The geopolymer cement slurry flows to the bottom of the wellbore through the casing, which will eventually be the pipe through which the hydrocarbons flow to the surface. From there, the geopolymer cement slurry fills in the space between the casing and the actual wellbore, and hardens. This creates a seal so that outside materials cannot enter the well flow, as well as permanently positions the casing in place. In preparing a well for cementing, it is important to establish the amount of cement required for the job. This may be done by measuring the diameter of the borehole along its depth, using a caliper log. Utilizing both mechanical and sonic means, multi-finger caliper logs measure the diameter of the well at numerous locations simultaneously in order to accommodate for irregularities in the wellbore diameter and determine the volume of the openhole. Additionally, the required physical properties of the cement are essential before commencing cementing operations. The proper set cement is also determined, including the density and viscosity of the material, before actually pumping the cement into the hole.

In some embodiments, curing the geopolymer cement slurry may refer to passively allowing time to pass under suitable conditions upon which the geopolymer cement slurry may harden or cure through allowing one or more reactions between the aqueous solution and the Saudi Arabian volcanic ash or cement precursor material, or both. Suitable conditions may be any time, temperature, pressure, humidity, and other appropriate conditions known in the cement industry to cure a cement composition. In some embodiments, suitable curing conditions may be ambient conditions. Curing may also involve actively hardening or curing the geopolymer cement slurry by, for instance, introducing a curing agent to the geopolymer cement slurry, providing heat or air to the geopolymer cement slurry, manipulating the environmental conditions of the geopolymer cement slurry to facilitate reactions between the aqueous solution and the Saudi Arabian volcanic ash or the cement precursor or both. Usually, the cement will be cured and convert from liquid to solid due to subsurface formation conditions, temperature, and pressure. In the laboratory, a curing chamber capable of applying temperature and pressure is used for curing the cement specimens at required conditions. Cubical molds (2″×2″×2″) and cylindrical cells (1.4″ diameter and 12″ length) were lowered into the curing chamber. Pressures and temperatures were maintained until shortly before the end of the curing where they were reduced to ambient conditions.

In some embodiments, curing may occur at a relative humidity of greater than or equal to 80% in the geopolymer cement slurry and a temperature of greater than or equal to 50° F. for a time period of from 1 to 14 days. Curing may occur at a relative humidity of from 80% to 100%, such as from 85% to 100%, or 90% to 100%, or from 95% to 100% relative humidity in the geopolymer cement slurry. The geopolymer cement slurry may be cured at temperatures of greater than or equal to 50° F., such as greater than or equal to 75° F., greater than or equal to 80° F., greater than or equal to 100° F., or greater than or equal to 120° F. The geopolymer cement slurry may be cured at temperatures of from 50° F. to 250° F., or from 50° F. to 200° F., or from 50° F. to 150° F., or from 50° F. to 120° F. In some instances, the temperature may be as great as 500° F. The geopolymer cement slurry may be cured for from 1 day to 14 days, such as from 3 to 14 days, or from 5 to 14 days, or from 7 to 14 days, or from 1 to 3 days, or from 3 to 7 days.

Further embodiments of the present disclosure relate to particular methods of cementing a casing in a wellbore. The method may include mixing an aqueous solution and Saudi Arabian volcanic ash or a cement precursor material, or both, to form a geopolymer cement slurry, introducing the geopolymer cement slurry into an annulus between the casing and the wellbore, and curing the geopolymer cement slurry to cement the casing in the wellbore.

Introducing the geopolymer cement slurry into an annulus may include pumping a geopolymer cement slurry into the annulus between a casing and a wellbore and curing the geopolymer cement slurry. The geopolymer cement slurry may be in accordance with any of the embodiments previously described. Likewise, curing the geopolymer cement slurry may be in accordance with any of the embodiments previously described. As stated previously, Cementing is performed when the geopolymer cement slurry is deployed into the well via pumps, displacing the drilling fluids still located within the well, and replacing them with cement. The geopolymer cement slurry flows to the bottom of the wellbore through the casing, which will eventually be the pipe through which the hydrocarbons flow to the surface. From there it fills in the space between the casing and the actual wellbore, and hardens. This creates a seal so that outside materials cannot enter the well flow, as well as permanently positions the casing in place.

The method may further comprise adding one or more additives selected from the group consisting of dispersants, fluid loss control agents, retarders, expansion additives, antifoaming agents, stabilizers, accelerators, extenders, weighting agents, lost circulation control agents, surfactants, gypsum, hematite, manganese tetroxide, silica flour, and silica sand.

Embodiments of the disclosure also relate to methods of producing cured geopolymer cements. The method may include combining aqueous solution with Saudi Arabian volcanic ash. The geopolymer cement slurry may be in accordance with any of the embodiments previously described. The method may include curing the geopolymer cement slurry by allowing for a reaction between the aqueous solution and the Saudi Arabian volcanic ash or the cement precursor material, or both, to produce cured geopolymer cement. The curing step may be in accordance with any of the embodiments previously described.

In some embodiments, cement is composed of four main components: tricalcium silicate (Ca₃O₅Si) which contributes to the early strength development; dicalcium silicate (Ca₂SiO₄), which contributes to the final strength, tricalcium aluminate (Ca₃Al₂O₆), which contributes to the early strength; and tetracalcium alumina ferrite. These phases are sometimes called alite and belite respectively. In addition, gypsum may be added to control the setting time of cement.

In one embodiment, the silicates phase in cement may be about 75-80 wt. % of the total material. Ca₃O₅Si is the major constituent, with concentration as great as 60-65 wt. %. The quantity of Ca₂SiO₄ conventionally does not exceed 20 wt. %, 30 wt. % or 40 wt. %. The hydration products for Ca₃O₅Si and Ca₂SiO₄ are calcium silicate hydrate (Ca₂H₂O₅Si) and calcium hydroxide (Ca(OH)₂), also known as Portlandite. The calcium silicate hydrate commonly called CSH gel has a variable C:S and H:S ratio depending on the temperature, calcium concentration in the aqueous phase, and the curing time. The CSH gel comprises +/−70% of fully hydrated Portland cement at ambient conditions and is considered the principal binder of hardened cement. By contrast, the calcium hydroxide is crystalline with concentration of about 15-20 wt. % and is the reason the cement has a pH of greater than 7. Upon contact with the aqueous solution, the gypsum may partially dissolve, releasing calcium and sulphate ions to react with the aluminate and hydroxyl ions produced by the C3A to form a calcium trisulphoaluminate hydrate, known as the mineral ettringite (Ca₆Al₂(SO₄)₃(OH)₁₂.26H₂O) that will precipitate onto the Ca₃O₅Si surfaces preventing further rapid hydration (flash-set). The gypsum is gradually consumed and ettringite continues to precipitate until the gypsum is consumed. The sulphates ion concentration will be drop down and the ettringite will become unstable converting to calcium monosulphoaluminate hydrate (Ca₄Al₂O₆(SO₄).14H₂O). The remaining unhydrated Ca₃O₅Si will form calcium aluminate hydrate. Geopolymer cement slurry design is based on the altering or inhibition of the hydration reactions with specific additives.

The cured geopolymer cement may include one or more of calcium hydroxide, silicates, oxides, belite (Ca₂SiO₅), alite (Ca₃SiO₄), tricalcium aluminate (Ca₃Al₂O₆), tetracalcium aluminoferrite (Ca₄Al₂Fe₂O₁₀), brownmilleriate (4CaO.Al₂O₃.Fe₂O₃), gypsum (CaSO₄.2H₂O) sodium oxide, potassium oxide, limestone, lime (calcium oxide), hexavalent chromium, trivalent chromium, calcium aluminate, other similar compounds, and combinations of these.

Without being bound by any particular theory, controlling the fluid loss and rheology properties of the geopolymer cement slurry when producing the cured geopolymer cement may result in a stronger, more stable cured geopolymer cement, as previously discussed. In some embodiments, the cured geopolymer cement of the present disclosure may have a compressive strength of from 1000 to 5000 pounds per square inch (psi) in the compressive Strength Test. In the test, the set cement cubes were removed from the molds, and placed in a hydraulic press where increasing force was exerted on each cubes until failure. The hydraulic press system used in this study applied known compressive loads to the samples. This system was designed to test the compressive strength of sample cement cubes in compliance with API specifications for oil wells cement testing.

In some embodiments, the geopolymer cement slurry may contain an aqueous solution and may be water-based. As such, the geopolymer cement slurry may by hydrophilic, forming stronger bonds with water-wet surfaces. Well sections drilled with non-aqueous drilling fluids may have oil-wet surfaces, resulting in poor bonding between the well and the geopolymer cement slurry, as oil and water naturally repel. Poor bonding may lead to poor isolation and a buildup of unwanted casing-casing or tubing-casing annular pressure. Without being bound by theory, it is desirable to make the subsurface formation water wet, the casing water wet, or both, to enhance and improve the bonding between cement and casing and cement and subsurface formation. If the wettability of the subsurface formation or casing is oil wet not water wet then the bonding will be poor and could result in small gap(s) or channel(s) between the cement and casing or the cement and subsurface formation thereby resulting in improper wellbore isolation. This improper wellbore isolation could lead to fluid or gas escaping from the well through this gas or channel due to de-bonding.

EXAMPLES Example 1

Wavelength Dispersive X-ray Fluorescence (WDXRF) may be used to conduct elemental analysis. In WDXRF spectrometers, all of the elements in the sample are excited simultaneously. The different energies of the characteristic radiation emitted from the sample are diffracted into different directions by an analyzing crystal or monochrometer (similar to the action of a prism dispersing different colors of visible light into different directions). By placing the detector at a certain angle, the intensity of X-rays with a certain wavelength can be measured. Sequential spectrometers use a moving detector on a goniometer to move it through an angular range to measure the intensities of many different wavelengths. Simultaneous spectrometers are equipped with a set of fixed detection systems, where each system measures the radiation of a specific element.

For the WDXRF analysis, a sample of Saudi Arabian volcanic ash was homogenized and manually grounded by an agate mortar and a pestle for several minutes to achieve fine particle size. Then, 4 grams of the Saudi Arabian volcanic ash powder was mixed well and homogenized with 0.9 grams of a binder (Licowax C micropowder PM (Hoechstwax)). Then, the powder was pressed with 20 tons of pressure to a pellet with 31 millimeter (mm) diameter. WDXRF analysis was then performed on the sample using the standardless Omnian 27 method. The composition is shown in Table 1 to be presented.

TABLE 1 Composition of Saudi Arabian Volcanic Ash Element Wt. % O 44.2 Si 21.8 Al 8.5 Fe 8.5 Ca 6.4 Mg 4.2 Na 3.1 Ti 1.5 K 1.0 P 0.3 Mn 0.1

The WDXRF results show that the sample consisted of mainly 0 and Si with appreciable amounts of Al, Fe, Ca, Mg, and Na.

Example 2

X-ray powder diffraction (XRD) is a rapid analytical technique primarily used for phase identification of a crystalline material and can provide information on unit cell dimensions. The analyzed material is finely ground, homogenized, and average bulk composition is determined. X-ray diffractometers consist of three basic elements: an X-ray tube, a sample holder, and an X-ray detector. X-rays are generated in a cathode ray tube by heating a filament to produce electrons, accelerating the electrons toward a target by applying a voltage, and bombarding the target material with electrons. When electrons have sufficient energy to dislodge inner shell electrons of the target material, characteristic X-ray spectra are produced. These spectra consist of several components, the most common being K_(α) and K_(β). K_(α) consists, in part, of K_(α1) and K_(α2). K_(α1) has a slightly shorter wavelength and twice the intensity as K_(α2). The specific wavelengths are characteristic of the target material (Cu, Fe, Mo, Cr). Filtering, by foils or crystal monochrometers, is required to produce the monochromatic X-rays needed for diffraction. K_(α1) and K_(α2) are sufficiently close in wavelength such that a weighted average of the two is used. These X-rays are collimated and directed onto the sample. As the sample and detector are rotated, the intensity of the reflected X-rays is recorded. A detector records and processes this X-ray signal and converts the signal to a count rate which is then output to a device such as a printer or computer monitor.

For the XRD analysis, a sample of Saudi Arabian volcanic ash was homogenized and manually grounded by an agate mortar and a pestle for several minutes to achieve fine particle size. Then, 4 grams of the fine Saudi Arabian volcanic ash powder was mounted into the XRD sample holder by back pressing. XRD was then performed on the sample using the SALAM 014 method. The composition is shown in Table 2 to be presented.

TABLE 2 XRD Composition of Saudi Arabian Volcanic Ash Compound Wt. % Amorphous Material 70 Labradorite: Ca_(0.65)Na_(0.32)(Al_(1.62)Si_(2.38)O₈) 19 Augite: Ca(Fe,Mg)Si₂O₆ 6 Forsterite: Mg₂SiO₄ 5

The XRD results show that the sample consisted mainly of amorphous material with appreciable amounts of labradorite, augite, and forsterite. The WDXRF results confirmed the XRD findings.

Example 3

Geopolymer cement slurries were made in accordance with the previous description. The compositions of these samples are described in the tables to be presented. Razeen® 2254 is available from Jubail Chemical Industries Company (headquartered in Jubail, Kingdom of Saudi Arabia) and includes Bisphenol-A-epichlorohydrin epoxy resin with the reactive diluent oxirane mono [(C12-C14)-alkyloxy)methyl] derivatives, has an epoxy equivalent weight of 190 to 210, a dynamic viscosity of 600 to 900 cP at 25° C., and a density of 1.11 g/cc at 25° C. Razeen® D 7106 is available from Jubail Chemical Industries Company, has an epoxy equivalent weight of 270 to 305, a dynamic viscosity of 7 to 15 cP at 25° C., and a density of 0.89 g/cc at 25° C. Le Supermul is a polyaminated fatty acid emulsifier available from Halliburton (headquartered in Houston, Tex.). Razeencure® 931 includes diethylenetriamine and is available from Jubail Chemical Industries Company.

TABLE 3 Composition of Resin Included in the Geopolymer Cement Slurry Component Amount Razeen ® 2254   80 g Razeen ® D 7106   20 g Le Supermul 7.75 g Razeen ® 931    3 g

TABLE 4 Compositions of the Geopolymer Cement Slurry with Resin and Comparative Examples 1, 2, 3, and 4 NaOH Saudi (6 Mol Arabian Re- Water A-3L solution) Volcanic tarder Component (mL) (Na₂SiO₃) (mL) Ash (g) Resin (g) Geopolymer 80   52 mL 28.2 300 110.75 g Cement (36.9 Slurry with wt. % Resin BWOV) Comparative 400 75.6 g 52.57 600 — Example 1 Comparative 350 75.6 g 52.57 600 — Example 2 Comparative 300 75.6 g 52.57 600 6 Example 3 Comparative 80 52.2 mL 28.2 300 — Example 4

Example 4

A-3L is commercially available from BJ Service Company Limited (headquartered in Houston, Tex.), and includes from 30% to 40% Na₂SiO₃. The retarder was HR®-5, available from Halliburton.

Physical properties of each comparative sample were then measured and are provided in the tables to be presented, where BHCT stands for Bottom Hole Circulating Temperature.

TABLE 5 Physical Properties for Geopolymer Cement Slurry with Resin and Comparative Examples 1, 2, 3, and 4 pH pH (Na₂SiO₃, Thickening BC (Na₂SiO₃ NaOH, Property Time BHCT Final Pressure Density and water) and water) Geopolymer — — — —  93 lb/ft³ 11.15 12.47 Cement Slurry with Resin Comparative 12 hours, 106° F. 100  2300 psi 105 lb/ft³ 12.40 13.04 Example 1 57 minutes Comparative — 106° F. 8 2400 psi 107 lb/ft³ 12.39 12.97 Example 2 Comparative — 106° F. 9 2400 psi 110 lb/ft³ 12.30 12.84 Example 3 Comparative — — — — 110 lb/ft³ 11.19 12.6 Example 4

TABLE 6 Viscometer Data for Geopolymer Cement Slurry with Resin and Comparative Examples 1 and 4 RPM 600 300 200 100 6 3 Geopolymer 200 125 98 71 12 8 Cement Slurry with Resin Comparative 37 20 15 9 3 3 Example 1 Comparative 91 52 40 28 21 19 Example 4

TABLE 7 Rheology Data for Geopolymer Cement Slurry with Resin and Comparative Examples 1 and 4 10 second gel 10 minute gel PV YP strength strength Geopolymer 75 cP 50 45 lbf/100 ft² 120 lbf/100 ft² Cement lbf/100 ft² Slurry with Resin Comparative 17 cP 3 lbf/100 ft²  3 lbf/100 ft²  18 lbf/100 ft² Example 1 Comparative 39 cP 13 31 lbf/100 ft² 110 lbf/100 ft² Example 4 lbf/100 ft²

The compressive strength for the geopolymer cement slurry with resin was measured by a hydraulic press with a destructive crush test using API RP 10B procedure. The compressive strength for the geopolymer cement slurry with resin was determined to be 2340 psi. The compressive strength for Comparative Example 4 was determined to be 2229 psi. Therefore, the geopolymer cement slurry with resin had a greater compressive strength than Comparative Example 4, which had the same composition as the geopolymer cement slurry with resin, except Comparative Example 4 did not have the resin. Additionally, the geopolymer cement slurry with resin outperformed Comparative Example 4 in PV, YP, 10 second gel strength, and 10 minute gel strength.

The geopolymer cement slurry with resin had a density of 93 lb/ft³, which is less than 170 lb/ft³, whereas conventional cement slurries conventionally have a density greater than 170 lb/ft³. It may be desirable to reduce the density of the geopolymer cement slurry to reduce the hydrostatic pressure exerted by the geopolymer cement slurry onto the subsurface formation. Additionally, it is desirable that the geopolymer cement slurry have a density of from 1 to 100 pcf, from 1 to 50 pcf, from 1 to 20 pcf, from 1 to 10 pcf, from 1 to 7 pcf, from 1 to 5 pcf, from 1 to 4 pcf, from 1 to 3 pcf, from 1 to 2 pcf, from 2 to 100 pcf, from 2 to 50 pcf, from 2 to 20 pcf, from 2 to 10 pcf, from 2 to 7 pcf, from 2 to 5 pcf, from 2 to 4 pcf, from 2 to 3 pcf, from 3 to 100 pcf, from 3 to 50 pcf, from 3 to 20 pcf, from 3 to 10 pcf, from 3 to 7 pcf, from 3 to 5 pcf, from 3 to 4 pcf, from 4 to 100 pcf, from 4 to 50 pcf, from 4 to 20 pcf, from 4 to 10 pcf, from 4 to 7 pcf, from 4 to 5 pcf, from 5 to 100 pcf, from 5 to 50 pcf, from 5 to 20 pcf, from 5 to 10 pcf, from 5 to 7 pcf, from 7 to 100 pcf, from 7 to 50 pcf, from 7 to 20 pcf, from 7 to 10 pcf, from 10 to 100 pcf, from 10 to 50 pcf, from 10 to 20 pcf, from 20 to 100 pcf, from 20 to 50 pcf, or from 50 to 100 pcf greater than the density of the subsurface formation. This may be desirable to avoid a kick.

Additionally, the geopolymer cement slurry with resin had a YP of 50 lbf/100 ft², which is greater than 20 lbf/100 ft², whereas conventional cement slurries conventionally have a density less than 20 lbf/100 ft². Having a density of less than 170 lb/ft³, and a yield point of greater than 20 lb/100 ft², may lead to consistent flowability and uniform placement of the geopolymer cement slurry with resin. It may be desirable to increase the yield point of the geopolymer cement slurry to reduce the penetration of the geopolymer cement slurry into the subsurface formation and to increase the reduction of lost circulation.

The thickening time for Comparative Example 1 was determined to be approximately 12 hours and 57 minutes at 106° F. and approximately 2300 psi, using a Chandler Engineering Consistometer Model 8340 according to API Spec 10 Code Schedule(1), API Recommended Practice 10B-2, and the Chandler Engineering Instruction Manual.

It is noted that one or more of the following claims utilize the term “where” or “in which” as a transitional phrase. For the purposes of defining the present technology, it is noted that this term is introduced in the claims as an open-ended transitional phrase that is used to introduce a recitation of a series of characteristics of the structure and should be interpreted in like manner as the more commonly used open-ended preamble term “comprising.” For the purposes of defining the present technology, the transitional phrase “consisting of” may be introduced in the claims as a closed preamble term limiting the scope of the claims to the recited components or steps and any naturally occurring impurities. For the purposes of defining the present technology, the transitional phrase “consisting essentially of” may be introduced in the claims to limit the scope of one or more claims to the recited elements, components, materials, or method steps as well as any non-recited elements, components, materials, or method steps that do not materially affect the novel characteristics of the claimed subject matter. The transitional phrases “consisting of” and “consisting essentially of” may be interpreted to be subsets of the open-ended transitional phrases, such as “comprising” and “including,” such that any use of an open ended phrase to introduce a recitation of a series of elements, components, materials, or steps should be interpreted to also disclose recitation of the series of elements, components, materials, or steps using the closed terms “consisting of” and “consisting essentially of.” For example, the recitation of a composition “comprising” components A, B, and C should be interpreted as also disclosing a composition “consisting of” components A, B, and C as well as a composition “consisting essentially of” components A, B, and C. Any quantitative value expressed in the present application may be considered to include open-ended embodiments consistent with the transitional phrases “comprising” or “including” as well as closed or partially closed embodiments consistent with the transitional phrases “consisting of” and “consisting essentially of.”

As used in the Specification and appended Claims, the singular forms “a”, “an”, and “the” include plural references unless the context clearly indicates otherwise. The verb “comprises” and its conjugated forms should be interpreted as referring to elements, components or steps in a non-exclusive manner. The referenced elements, components or steps may be present, utilized or combined with other elements, components or steps not expressly referenced.

It should be understood that any two quantitative values assigned to a property may constitute a range of that property, and all combinations of ranges formed from all stated quantitative values of a given property are contemplated in this disclosure. The subject matter of the present disclosure has been described in detail and by reference to specific embodiments. It should be understood that any detailed description of a component or feature of an embodiment does not necessarily imply that the component or feature is essential to the particular embodiment or to any other embodiment.

It should be apparent to those skilled in the art that various modifications and variations may be made to the embodiments described within without departing from the spirit and scope of the claimed subject matter. Thus, it is intended that the specification cover the modifications and variations of the various embodiments described within provided such modification and variations come within the scope of the appended claims and their equivalents. Unless otherwise stated within the application, all tests, properties, and experiments are conducted at room temperature and atmospheric pressure.

Having described the subject matter of the present disclosure in detail and by reference to specific embodiments of any of these, it is noted that the various details disclosed within should not be taken to imply that these details relate to elements that are essential components of the various embodiments described within, even in cases where a particular element is illustrated in each of the drawings that accompany the present description. Further, it should be apparent that modifications and variations are possible without departing from the scope of the present disclosure, including, but not limited to, embodiments defined in the appended claims. More specifically, although some aspects of the present disclosure are identified as particularly advantageous, it is contemplated that the present disclosure is not necessarily limited to these aspects. 

What is claimed is:
 1. A geopolymer cement slurry comprising: an aqueous solution; Saudi Arabian volcanic ash, in which the Saudi Arabian volcanic ash comprises SO₃, CaO, SiO₂, Al₂O₃, Fe₂O₃, MgO, and K₂O; Na₂SiO₃; NaOH; and a resin.
 2. The geopolymer cement slurry of claim 1, in which the geopolymer cement slurry comprises from 25 to 50 wt. % Na₂SiO₃ and 15 to 35 wt. % NaOH.
 3. The geopolymer cement slurry of claim 1, in which the Na₂SiO₃ has a ratio of Na₂O to SiO₂ of from 0.250:1 to 0.350:1.
 4. The geopolymer cement slurry of claim 1, in which the geopolymer cement slurry comprises a pH of from 11.6-13.0.
 5. The geopolymer cement slurry of claim 1, in which the Saudi Arabian volcanic ash has a particle size of from 20 to 30 μm.
 6. The geopolymer cement slurry of claim 1, in which the Saudi Arabian volcanic ash is free of TiO₂.
 7. The geopolymer cement slurry of claim 1, in which the Saudi Arabian volcanic ash comprises from 40 wt. % to 50 wt. % SiO₂ and from 10 wt. % to 20 wt. % Al₂O₃.
 8. The geopolymer cement slurry of claim 1, in which the Saudi Arabian volcanic ash comprises: from 0.05 wt. % to 0.2 wt. % SO₃; from 5 wt. % to 10 wt. % CaO; from 40 wt. % to 50 wt. % SiO₂; from 10 wt. % to 20 wt. % Al₂O₃; from 10 wt. % to 15 wt. % Fe₂O₃; from 5 wt. % to 10 wt. % MgO; and from 0.5 wt. % to 5 wt. % K₂O.
 9. The geopolymer cement slurry of claim 1, in which the geopolymer cement slurry comprises 10 to 30 wt. % resin.
 10. The geopolymer cement slurry of claim 1, in which the resin comprises bisphenol-A-epichlorohydrin epoxy; 2,3-epoxypropyl-o-tolyl ether; alkyl glycidyl ether; 1,6-hexanediol diglycidyl ether; butyl glycidyl ether; cyclohexanedimethanol; cyclohexanedimethanol diclydicyl ether; or combinations of these.
 11. The geopolymer cement slurry of claim 1, in which the geopolymer cement slurry comprises a sodium aluminosilicate hydrate having a formula of: Na_(n)[(—SiO₂)_(z)—AlO₂]_(n).y H₂O, where n represents a degree of polymerization ranging 1 to 50 and z represents an amount of silicate ranging from 2 to 10
 12. The geopolymer cement slurry of claim 1, in which the geopolymer cement slurry comprises a sodium aluminosilicate hydrate having a structure of:


13. The geopolymer cement slurry of claim 1, in which the geopolymer cement slurry has a ratio of Na₂SiO₃ combined with NaOH to Al₂O₃ ranges from 0.5:1.0 to 7.0:1.0.
 14. The geopolymer cement slurry of claim 1, in which aqueous solution comprises deionized water, tap water, fresh water, salt water, natural or synthetic brine, municipal water, formation water, produced water, well water, filtered water, distilled water, sea water, or combinations of these.
 15. The geopolymer cement slurry of claim 1, in which the geopolymer cement slurry comprises from 30 to 60 wt. % Saudi Arabian volcanic ash.
 16. The geopolymer cement slurry of claim 1, in which the geopolymer cement slurry further comprises a cement precursor material comprising one or more components selected from the group consisting of calcium hydroxide, silicates, belite (Ca₂SiO₅), alite (Ca₃SiO₄), tricalcium aluminate (Ca₃Al₂O₆), tetracalcium aluminoferrite (Ca₄Al₂Fe₂O₁₀), brownmillerite (4CaO.Al₂O₃.Fe₂O₃), gypsum (CaSO₄.2H₂O), sodium oxide, potassium oxide, lime (calcium oxide), hexavalent chromium, trivalent chromium, calcium aluminate, and combinations thereof.
 17. The geopolymer cement slurry of claim 1, in which the geopolymer cement slurry further comprises one or more additives selected from the group consisting of dispersants, fluid loss control agents, retarders, expansion additives, antifoaming agents, stabilizers, accelerators, extenders, weighting agents, lost circulation control agents, surfactants, gypsum, hematite, manganese tetroxide, silica flour, and silica sand.
 18. The geopolymer cement slurry of claim 1, in which the geopolymer cement slurry further comprises a curing agent comprising diethylenetriamine, diethyltoluenediamine, polyoxypropylene diamine, or combinations of these. 